Crystalline Modification of Fipronil

ABSTRACT

The present invention relates to a crystalline modification of fipronil, to a process for the preparation of the same, to pesticidal and parasiticidal mixtures and compositions comprising said crystalline modification and to their use for combating pests and parasites.

The present invention relates to a novel crystalline modification offipronil, to a process for the preparation of the same, to pesticidaland parasiticidal mixtures and compositions comprising said crystallinemodification and to their use for combating pests and parasites.

Fipronil (formula I) is an active compound for controlling certaininsect and acarid pests, and parasites.

Various processes for the preparation of fipronil have been described,generally and in detail. Documents which give detailed preparationprocedures are e.g. EP 295 117; EP 460 940; EP 484 165; EP 668 269; EP967 206; EP 1 331 222; EP 1 374 061; U.S. Pat. No. 5,631,381; CN1374298; or J. of Heibei University of Science and Technology, Vol. (2),Sum 69 (2004), Dok. Serial No. 1008-1542 (2004) 02-0018-03.

Characterization of the fipronil material obtained by the processesdescribed in the prior art is usually done by ¹H-NMR analysis and/ormeasurement of the melting point. The described melting points are inthe range of from 187° C. to 203° C., mostly in the range of from 195°C. to 203° C. In the Pesticidal Manual, 13th Edition (2003), BritishCrop Protection Council, p. 433, fipronil is described as a white solidwith a melting point of 200 to 201° C., with technical fipronil having amelting point of 195.5° C. to 203° C. Observations of differentcrystalline forms of fipronil have not been described, let alone anycharacterization of a certain crystalline modification or a preparationprocedure for obtaining a certain crystalline modification.

For the large-scale preparation and formulation of a market compoundsuch as fipronil, it is of crucial importance to know whether differentcrystalline modifications (also frequently referred to as polymoprhs) ofa compound exist, how they can be obtained, and what theircharacteristic properties are. Crystalline modifications of one compoundmay have very different properties, for example with regard tosolubility, rate of dissolution, suspension stability, stability duringgrinding, vapour pressure, optical and mechanical properties,hygroscopicity, crystal size, filtration properties, desiccation,density, melting point, degradation stability, stability against phasetransformation into other crystalline modifications, colour, and evenchemical reactivity.

For example, different crystalline modifications frequently manifestthemselves in different forms of the crystals, such as needles orplates. This is of relevance for e.g a filtration step in thepreparation procedure. Plates typically will clog the pores of a filterleading to loss of time and product and tedious and expensive cleaningwork. Also, a crystalline modification being present as plates and acrystalline modification being present as needles can have significantlydifferent bulk densities which has implications for storage andpackaging. Another relevant aspect, especially in the production ofpesticides, is whether the crystalline modification is present as a finepowder which can produce hazardous dusts, or as dust-free largercrystals.

Against this background, it has been an object of the present inventionto find and characterize a novel crystalline modification of fipronil.

A further object has been to find preparation procedures for the novelcrystalline modification which reproducibly give the crystallinemodification.

Another object of the invention has been to find preparation procedureswhich give the novel crystalline modification II in high yield.

Yet another object of the invention has been to find preparationprocedures which give the novel crystalline modification essentiallyexcluding other crystalline modification forms (i.e. in over 80% byweight).

Accordingly, a novel crystalline modification of fipronil, a process forits preparation, pesticidal and parasiticidal mixtures and compositionscomprising it and its use for combating pests and parasites has beenfound. The novel crystalline modification of fipronil is defined as“novel crystalline modification II” throughout this application. It ispresent as long needles which provides for its easy filtration.

Also, most suprisingly, 3 other crystalline modifications of fipronilhave been found, which are subject to co-pending patent applications.Especially surprising was that the present crystalline modification IIof fipronil does not melt but rather undergoes a phase transformationduring heating into two thermodynamically more stable forms I and Vand/or a mixture of them, and thus in a typical melting pointmeasurement will give the melting points of these forms I and V ormixtures of them. Crystalline modification I has a very similar meltingpoint as a second crystalline modification V (as described in co-pendingpatent applications), both melting points lying in the range of themelting points given in the prior art (i.e. 195 to 203° C.). Moreover,one further crystalline modification IV of fipronil, as described in aco-pending patent application, also undergoes a phase transformation.The solid forms of fipronil thus are part of a very complexcrystallization scenario. It can be concluded that the melting pointsgiven in the literature in no way can indicate which crystallinemodification or crystalline modification mixtures were analyzed.

In T 605/02, the Technical Board of Appeal of the European PatentAuthority ruled that, in the absence of a respective describedpreparation procedure, even the XRD pattern of a certain crystallinemodification does not constitute prior art for lack of enablement. Thus,melting points given in documents published prior to the filing of thisapplication cannot be regarded as prior art for the present invention asthey do not enable the artisan to prepare the novel crystallinemodification of fipronil.

Crystalline modification II of fipronil, in an X-ray powderdiffractogram at 25° C., shows at least 4, in particular at least 5,especially 7 and preferably all of the following reflexes:

(1) d = 13.44 ± 0.2 Å 2Θ = 6.6 ± 0.2° (2) d = 7.84 ± 0.1 Å 2Θ = 11.3 ±0.2° (3) d = 5.50 ± 0.07 Å 2Θ = 16.1 ± 0.2° (4) d = 5.14 ± 0.05 Å 2Θ =17.2 ± 0.2° (5) d = 4.95 ± 0.05 Å 2Θ = 17.9 ± 0.2° (6) d = 3.95 ± 0.05 Å2Θ = 22.4 ± 0.2° (7) d = 3.77 ± 0.05 Å. 2Θ = 23.5 ± 0.2° (8) d = 3.22 ±0.03 Å 2Θ = 27.6 ± 0.2° (9) d = 2.91 ± 0.03 Å 2Θ = 30.8 ± 0.2°.

In a particularly preferred embodiment, the crystalline modification IIexhibits a powder X-ray diffraction pattern substantially the same asthe pattern shown in FIG. 1.

Studies of single crystals of the crystalline modification II have shownthat the crystal system is monoclinic and has the space group P 2(1)/c.The characteristic data of the crystal structure of the crystallinemodification II are shown in Table 1:

TABLE 1 Crystallographic data and parameters of the crystallinemodification II measured from Parameter Modification II Class MonoclinicSpace group P 2(1)/c a  8.606(1) Å b 26.919(2) Å C 16.086(1) Å α 90° β102.066(1)° γ 90° Volume 3644.0(3) Å³ Z 4 Temperature −173.2° C. Density(calculated) 0.94 g/cm^(3a) R1, ωR2 0.081, 0.222 a, b, c = Length of theunit cell edges α, β, γ = Angles of the unit cell Z = Number ofmolecules in the unit cell ^(a)Density calculated without theincorporated solvent

The single crystal structure further reveals, that modification II offipronil has channel like tubes running through the crystal. These tubesare occupied by the corresponding crystallization solvent. This affectsthe powder diffraction patterns in a way that the X-ray reflections canbe seen at slightly different 2Theta and d-spacing values (not more than±0.34° 2Theta) for many of the solvates. The peak intensities areindependent of the incorporated solvent[B1]. Modification II cantherefore be regarded as a solvate of the corresponding co-crystallizedsolvent.

As the solvents trapped in the crystal are removed, the crystallinemodification II of fipronil undergoes an endothermic phasetransformation. In a differential scanning calorimetry, DSC, measurement(heating rate 5 K/min) this is observed typically at around 130° C.,with an onset at 100 to 110° C. and completion at 138° C. to 145° C.This phase transformation leads to crystalline modifications I and Vand/or depending on the heating rate to mixtures of them. We give hereas an example a differential scanning calorimetry (DSC) thermogram ofthe crystalline modification II of fipronil, recorded with 10 K/min. Itfurther contains two endotherms with maxima at 196° C. and 203° C.,representing the melting points of the crystalline modifications I (mp.196° C.) and V (mp. 203° C.) of fipronil. It is shown in FIG. 2.

Solvents in the process for preparation of modification II are inert andconsist mainly of benzene derivatives, such as benzene, which may besubstituted by one or more groups selected from halogen, cyano,C₁-C₆-alkyl, C₁-C₆-alkoxy, halogenmethyl, and nitro, and other solvents,such as tetrahydrofuran (THF), 1,2-dichloroethane, and acetonitrile.Preferred benzene derivatives are fluorobenzene, benzonitrile, anisole,p-xylene, o-xylene, m-xylene, CF₃-benzene, n-butylbenzene,t-butylbenzene, s-butyl-benzene, i-butylbenzene, chlorobenzene,2-chlorotoluene, 4-chlorotoluene, 1,2-dichlorobenzene,1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,4-diisopropylbenzene,mesitylene, nitrobenzene, 4-nitrotoluene, n-propylbenzene, and toluene,and more preferably selected from mono-, di- or tri(C₁-C₆-alkyl)benzenes[B2], which may be halogenated.

The crystalline modification II of fipronil can be achieved preferablyfrom the following solvents; tetrahydrofuran, 1,2-dichloroethane,acetonitrile, toluene, mono chloro benzene, 1,2-dichlorobenzene, ethylbenzene, mesitylene, nitrobenzene and CF₃-benzene.

The amount of co-crystallized solvent depends of the properties, such assize of the corresponding solvent. For toluene the maximum amount ofsolvent in the crystals is in the range of 5 w-%. The solvent amount canbe analysed for example via thermogravimetry. A TGA-trace of crystallinefipronil modification II from toluene is shown in FIG. 3.

In addition to the various solvent adduct versions of modification II,it was further discovered, that from all of the above mentioned solventsalso at least one other crystalline modification can be achieved viasolvent crystallization. Several conditions lead also to mixtures offorms, but also polymorph or modification pure material can be preparedby applying delicate and controlled, solvent dependant methods. Theapplicant has described preparation methods of modifications I and V inco-pending patent applications[B3].

Also a further modification F-ST, a toluene solvate, is described inWO2007/069254. This solvate modification F-ST is different from the heredescribed novel modification II which also contains co-crystallizedtoluene. This should be made clear by comparison of the powderdiffraction patterns[B4] shown in FIG. 1, and in WO2007/069254. Itappears that F-ST is a stoichiometric solvate of fipronil and toluene inthe ratio of about 2:1 respectively. In the case of toluene this meansthat there is about 8 w-% of toluene in the crystal lattice, which isabout 3 w-% more than for crystalline modification II according to thecurrent invention.

Further, structurally similar solvates to F-ST form can be prepared alsowith benzene, mono chloro benzene (MCB) as well as xylene (mixture).

Similar to F-ST, also crystalline modification II of fipronil can beused as starting material to prepare pure modification V via drying(tempering) above 100° C., preferably above 130° C. The drying timedepends of the applied pressure. As modification II contains lesstoluene than F-ST, also less energy is needed in the drying (tempering)process.

In another embodiment, the present invention relates to the crystallinemodification II having a fipronil content of at least 92% by weight,particularly at least 96% by weight and especially at least 98% byweight.

This invention also relates to solid (compositions of) fipronilcomprising the crystalline modification II as defined hereinabove and aform of fipronil being different from said crystalline modification II(herein also referred to as “fipronil form”), e.g. amorphous fipronil orfipronil of a crystalline modification different from crystallinemodification II. Preferably, the solid (compositions of) fipronilcomprise the crystalline modification II in at least 85% by weight,preferably in at least 90% by weight, more preferably in at least 95% byweight, and most preferably in at least 98% by weight[B6].

The crystalline modification II can be prepared using a process whichcomprises the following steps:

-   -   step i) preparing a solution of a solid form of fipronil being        different from the crystalline modification II in a solvent S        preferably selected from tetrahydrofurane (THF),        1,2-dichloroethane (DCE), acetonitrile, toluene,        monochlorobenzene (MCB), 1,2-dichlorobenzene (DCB), ethyl        benzene, mesitylene, nitrobenzene and CF₃-benzene;    -   step ii) effecting crystallization of fipronil; and    -   step iii) isolating the resulting precipitate.

The preparation of modification II is favored by crystallization fromconcentrated solutions at elevated temperatures. Further, the resultingmodification is dependent of especially the nucleation temperaturefollowed by the formation of the first crystals. The beginning of thecrystallization can be detected visually as clouding of thecrystallization solution and/or with the aid of a turbidity probe.Usually the evaporation or cooling crystallisation is effected not above130° C., or close to the boiling point of the used solvent, andpreferably not below 80° C.

Thus crystallization of modification II can be done by crystallizationof fipronil from the aforesaid solvents at constant temperature byevaporation and/or by adding at least a polar solvent P to the abovementioned aromatic solvents. Such cooling cystallisation isadvantageously started at a temperature close to the boiling point ofthe solvent, however, preferably not above 130° C. or below 80° C. Moreprecisely in the cases of THF, 1,2-dichloroethane and acetonitrile thecrystallization temperature in an evaporation crystallization should bekept within a temperature window of 30 and 55° C., for toluene within atemperature window of 90° C. to 110° C., for MCB and 1,2-dichlorobenzenein between 70° C. and 130° C., nitrobenzene and mesitylene in between90° C. and 130° C. and for ethyl benzene in between 100° C. and 130° C.and for CF₃-benzene in between 90° C. and 103° C.

Modification II can also be crystallised from mixtures of the abovementioned aromatic solvents and polar solvents P, advantageously inamounts up to 20 vol.-%, preferably 5 to 15 vol.-% of P. Such solvent Pis preferably selected from the group of methanol, ethanol, propan-1-ol,propan-2-ol (isopropanol), butan-1-ol (n-butanol), butan-2-ol,tert-butanol, 2-methyl-propan-1-ol (iso-butanol), 2-methyl-propan-2-ol,pentan-3-ol, 2-methyl butan-1-ol, 3-methyl butan-1-ol, 1,2-ethanediol,1,3-propandiol, 1,2-propandiol, cyclohexanol, acetonitrile,propionitrile, acetone, butanone (methyl ethyl ketone), pentan-2-one(methyl propyl ketone), pentan-3-one (diethylketone),4-methyl-2-pentanone (isobutyl-methyl-ketone), 3-methyl-butan-2-one(iso-propyl-methyl-ketone), 3,3-dimethyl-2-butanone(tert-butyl-methyl-ketone), cyclohexanone, methylacetate, ethylacetate,isopropylacetate, N-butylacetate, isobutylacetate, diethylcarbonate,2-butoxyethylacetate, dioxane, THF, diethylether, 2-methyl-THF,methyl-tert-butylether, dimethylformamide, dimethylacetamide,dimethylsulfoxide (DMSO), nitromethane, and nitroethane.

Modification II can also be crystallized by effecting thecrystallization by cooling concentrated solutions of the correspondingsolvent. In a cooling crystallization the crystallization begin needs tobe within the aforesaid temperature ranges. Parameters effecting thenucleation temperature and beginning of crystallization areconcentration, cooling rate and time of adding possible seeding crystalsof the wanted modification to a supersaturated solution. Theconcentration depends naturally of the solubility of fipronil in thecorresponding solvent. The cooling rate is typically in between 5 K/hand 20 K/h. The cooling rate may not exceed 1 K/minute.

A person skilled in the art is able to perform a cooling crystallizationin a corresponding solvent so that these conditions are met.

If the crystallization is not affected in a way that the nucleationbegins in the aforesaid narrow temperature ranges, other modificationsor mixtures of modifications result.

Modification II can be obtained from a solution in THF, or DCE byevaporation at from 40° C. to the boiling point of the solvent used.Evaporation from a THF solution at 20-25° C. yield a mixture ofmodifications I and II.

Alternatively modification II is obtainable from a solution inacetonitrile by cooling crystallization from 80 to 5° C. (cf. example4).

In a further embodiment of the invention modification II is obtainablefrom a solution in toluene by a cooling crystallization when nucleationand crystallization starts above 90° C. (cf. example 5). In between 90and 75° C. mixtures of II and III (F-ST) result.

In a further embodiment of the invention modification II is obtainablefrom a solution in monochlorobenzene (MCB) also in a coolingcrystallization (cf. example 6).

In a further embodiment of the invention modification II is obtainablefrom a solution in mesitylene (cf. example 7).

In a further embodiment of the invention modification II is obtainablefrom a solution in dichlorobenzene (DCB) in two concentrations.

In a further embodiment of the invention modification II is obtainablefrom a solution in nitrobenzene (cf. example 8).

In a further embodiment of the invention modification II is obtainablefrom a solution in ethyl benzene when crystallization took place above100° C. (cf. example 9). Preferably solutions with a fipronil content of10 w.-% or more, more preferably of 15 w.-% or more are used.

In a further embodiment of the invention modification II is obtainablefrom a solution in CF₃-benzene at 90° C. or more, preferably 95° C. orabove.

A detailed description of these steps is as follows:

Step i)

Suitable fipronil forms different from the crystalline modification IIused in step i) are, for example, selected from amorphous fipronil orcrystalline fipronil such as other triclinic or monoclinic forms, e.g.monoclinic fipronil of the space group C2/c, and also mixtures ofcrystalline modifications of fipronil.

The fipronil form used as starting material in step i) preferably has apurity of at least 85% by weight, in particular at least 90% by weightand especially at least 95% by weight. “Purity” means the absence ofchemical compounds other than fipronil.

The solvent S used in step i) consists of either acetonitrile, DCB, DCE,ethyl benzene, MCB, mesitylene, nitrobenzene, THF, toluene, orCF₃-benzene, each pure or in combination with a polar solvent P.

In a preferred embodiment, the solvent S used in step i) consists ofDCB, mesitylene, and nitrobenzene, each pure or in combination with apolar solvent P

In another preferred embodiment, the solvent S used in step i) consistsof ethyl benzene, MCB, and toluene, each pure or in combination with apolar solvent P In step i), the fipronil form different from thecrystalline modification II will usually be incorporated into thesolvent S as a solid with mixing at a concentration and temperaturewhere the solvent S is capable of completely dissolving the fipronilform.

The amount of fipronil form dissolved in the solvent S depends, on thenature of the solvent S and on the dissolution temperature. The personskilled in the art will be able to determine suitable conditions bystandard experiments.

Step ii)

In step ii) of the process of this invention, fipronil is thencrystallized. Crystallization can be effected in a customary manner, forexample by cooling the solution obtained in step i), by adding a solventwhich reduces the solubility, or by concentrating the solution, or by acombination of the measures mentioned above.

In a preferred embodiment, step ii) is carried out in the presence ofseed crystals of the crystalline modification II.

To achieve a conversion into the crystalline modification II which is ascomplete as possible, the crystallization is carried out over a period(duration of crystallization) of at least 1 h, in particular at least 3h. Duration of crystallization is understood by the person skilled inthe art as meaning the period of time between the beginning of themeasure which initiates crystallization and the isolation of thefipronil by separating the crystalline material from the mother liquor.

In general, the crystallization is allowed to proceed to a point whereat least 60%, preferably at least 70%, in particular at least 90% byweight, for example from 80 to 90% by weight, of the fipronil employedhas crystallized out.

Concentration of the solution is effected by gradually removing thesolvent S, such as by evaporation in vacuo, either at low temperature orat about 20° C. to 25° C. or at elevated temperature, and/or in thepresence of a flow of an inert gas such as nitrogen or argon. The valuesof “low temperature” and “elevated temperature” depend, on the nature ofthe solvent S, however should not exceed 60° C.

In a preferred embodiment, the crystallization is effected byconcentrating the solution.

Step iii)

In step iii) of the process of this invention, the crystallinemodification II is isolated using customary techniques for separatingsolid components from liquids, for example by filtration, centrifugationor decanting. In general, the isolated precipitate will be washed, forexample with the solvent S used for the crystallization. The washing canbe carried out in one or more steps. The washing is typically carriedout at temperatures lower than 30° C. and in particular lower than 25°C., to keep the loss of the product of value as low as possible. Theresulting crystalline fipronil or modification II can then be dried andsubjected to further processing.

The preparation process consisting of steps i) to step iii) can berepeated in order to achieve higher purities of fipronil.

The crystalline modification II is especially suitable for efficientlycombating the following pests:

millipedes (Diplopoda) such as Blaniulus or Narceus ssp;insects (Insecta) such as:ants, bees, wasps, sawflies (Hymenoptera), e.g. Atta capiguara, Attacephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana,Crematogaster spp., Hoplocampa minuta, Hoplocampa testudinea, Monomoriumpharaonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri,Solenopsis xyloni, Pheidole megacephala, Pogonomyrmex species such asPogonomyrmex barbatus and Pogonomyrmex californicus, Dasymutillaoccidentalis, Bombus spp. Vespula squamosa, Paravespula vulgaris,Paravespula pennsylvanica, Paravespula germanica, Dolichovespulamaculata, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, andLinepithema humile,beetles (Coleoptera), such as Agrilus sinuatus, Agriotes lineatus,Agriotes obscurus and other Agriotes species, Amphimallus solstitialis,Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aracanthusmorei, Atomaria linearis, Blapstinus species, Blastophagus piniperda,Blitophaga undata, Bothynoderes punciventris, Bruchus rufimanus, Bruchuspisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotomatrifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnematibialis, Conoderus vespertinus and other Conoderus species,Conorhynchus mendicus, Crioceris asparagi, Cylindrocopturus adspersus,Diabrotica (longicornis) barberi, Diabrotica semi-punctata, Diabroticaspeciosa, Diabrotica undecimpunctata, Diabrotica virgifera and otherDiabrotica species, Eleodes species, Epilachna varivestis, Epitrixhirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hyperabrunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lemamelanopus, Leptinotarsa decemlineata, Limonius californicus and otherLimonius species, Lissorhoptrus oryzophilus, Listronotus bonariensis,Melanotus communis and other Melanotus species, Meligethes aeneus,Melolontha hippocastani, Melolontha melolontha, Oulema oryzae,Ortiorrhynchus sulcatus, Oryzophagus oryzae, Otiorrhynchus ovatus,Oulema oryzae, Phaedon cochleariae, Phyllotreta chrysocephala,Phyllophaga cuyabana and other Phyllophaga species, Phylloperthahorticola, Phyllotreta nemorum, Phyllotreta striolata, and otherPhyllotreta species, Popillia japonica, Promecops carinicollis,Premnotrypes voraz, Psylliodes species, Sitona lineatus, Sitophilusgranaria, Sternechus pinguis, Sternechus subsignatus, and Tanymechuspalliatus and other Tanymechus species,Centipedes (Chilopoda), e.g. Scutigera coleoptrata,Cockroaches (Blattaria-Blattodea), e.g. Blattella germanica, Blattellaasahinae, Periplaneta americana, Periplaneta japonica, Periplanetabrunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blattaorientalis,Crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica,Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus,Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes,Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana,Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus,Oedaleus senegalensis, Zonozerus variegatus, Hieroglyphus daganensis,Kraussaria angulifera, Calliptamus italicus, Chortoicetes terminifera,and Locustana pardalina,fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis,Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllusfasciatus,Flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedesvexans, Agromyza oryzea, Anastrepha ludens, Anopheles maculipennis,Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anophelesfreeborni, Anopheles leucosphyrus, Anopheles minimus, Anophelesquadrimaculatus, Calliphora vicina, Chrysomya bezziana, Chrysomyahominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea,Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola,Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culexnigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata,Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae,Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobiahominis, Fannia canicularis, Gasterophilus intestinalis, GeomyzaTripunctata, Glossina morsitans, Glossina palpalis, Glossina fuscipes,Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris,Hippelates spp., Hypoderma lineata, Leptoconops torrens, Liriomyzasativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Luciliasericata, Lycoria pectoralis, Mansonia spp., Mayetiola destructor, Muscadomestica, Muscina stabulans, Oestrus ovis, Oestrus ovis, Opomyzaflorum, Oscinella frit, Pegomya hysocyami, Phlebotomus argentipes,Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Progonyaleyoscianii, Psila rosae, Psorophora columbiae, Psorophora discolor,Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophagahaemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans,Tabanus bovinus, Tabanus atratus, Tabanus lineola, Tabanus similis,Tetanops myopaeformis, Tipula olerace, and Tipula paludosa,Heteropterans (Heteroptera), such as Acrosternum hilare, Blissusleucopterus, Cicadellidae such as Empoasca fabae, Chrysomelidae,Cyrtopeltis notatus, Delpahcidae, Dysdercus cingulatus, Dysdercusintermedius, Eurygaster integriceps, Euschistus impictiventris,Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nephotettixspecies, Nezara viridula, Pentatomidae, Piesma quadrata, Solubeainsularis and Thyanta perditor,Aphids and other homopterans (Homoptera), e.g. Acyrthosiphon onobrychis,Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphisglycines, Aphis gossypii, Aphis grossulariae, Aphis pomi, Aphisschneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum,Aulacorthum solani, Brachycaudus cardui, Brachycaudus helichrysi,Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae,Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii,Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphisradicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphispyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae,Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megouraviciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzodes(Myzus)persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonoviaribis-nigri, Nilaparvata lugens, Pemphigus bursarius, Pemphiguspopulivenae, and other Pemphigus species, Perkinsiella saccharicida,Phorodon humuli, Psyllidae such as Psylla mali, Psylla piri and otherPsylla species, Rhopalomyzus ascalonicus, Rhopalosiphum maidis,Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphismali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae,Trialeurodes vaporariorum, Toxoptera aurantiiand, and Viteus vitifolii,Lepidopterans (Lepidoptera), for example Agrotis ypsilon, Agrotissegetum and other Agrotis species, Alabama argillacea, Anticarsiagemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius,Cacoecia murinana, Capua reticulana, Chematobia brumata, Chilosuppresalis and other Chilo species, Choristoneura fumiferana,Choristoneura occidentalis, Cirphis unipuncta, Cnaphlocrocis medinalis,Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraeagrandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoeciliaambiguella, Euxoa species, Evetria bouliana, Feltia subterranea,Galleria mellonella, Grapholitha funebrana, Grapholitha molesta,Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis,Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferialycopersicella, Lambdina fiscellaria, Laphygma exigua, Lerodea eufala,Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella,Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantriamonacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae,Momphidae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea,Pectinophora gossypiella, Peridroma saucia, Phalera bucephala,Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae,Plathypena scabra, Plutella xylostella, Pseudoplusia includens,Rhyacionia frustrana, Scrobipalpula absoluta, Sesamia nonagrioides andother Sesamia species, Sitotroga cerealella, Sparganothis pilleriana,Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura,Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni andZeiraphera canadensis,lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanuscorporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis,Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthusstramineus and Solenopotes capillatus,orthopterans (Orthoptera), such as Acrididae, Acheta domestica,Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria,Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus,Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata,Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanusand Tachycines asynamorus,silverfish, firebrat (Thysanura), e.g. Lepisma saccharina and Thermobiadomestica,termites (Isoptera), such as Calotermes flavicollis, Coptotermes ssp.,Dalbulus maidis, Heterotermes aureus, Leucotermes flavipes, Macrotermesgilvus, Reticulitermes ssp., Termes natalensis, Coptotermes formosanus,thrips (Thysanoptera), such as Frankliniella fusca, Frankliniellaoccidentalis, Frankliniella tritici and other Frankliniella species,Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips simplex, andThrips tabaci,ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g. Ixodesscapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalussanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyommaamericanum, Ambryomma maculatum, Ornithodorus hermsi, Ornithodorusturicata and parasitic mites (Mesostigmata), e.g. Ornithonyssus bacotiand Dermanyssus gallinae,true bugs (Hemiptera), e.g. Cimex lectularius, Cimex hemipterus,Reduvius senilis, Triatoma spp., Rhodnius prolixus, and Arilus critatus,Arachnoidea, such as arachnids (Acarina), for example of the familiesArgasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum,Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilusdecoloratus, Boophilus microplus, Dermacentor silvarum, Hyalommatruncatum, Ixodes ricinus, Ixodes rubicundus, Latrodectus mactans,Loxosceles reclusa, Ornithodorus moubata, Otobius megnini, Dermanyssusgallinae, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalusevertsi, Sarcoptes scabiei, and Eriophyidae species such as Aculusschlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni;Tarsonemidae species such as Phytonemus pallidus and Polyphagotarsonemuslatus; Tenuipalpidae species such as Brevipalpus phoenicis;Tetranychidae species such as Tetranychus cinnabarinus, Tetranychuskanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychusurticae, Panonychus ulmi, Panonychus citri, and Oligonychus pratensis,Earwigs (Dermaptera), e.g. forficula auricularia; andNematodes, including plant parasitic nematodes and nematodes living inthe soil. Plant parasitic nematodes include, such as root knotnematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogynejavanica, and other Meloidogyne species; cyst-forming nematodes,Globodera rostochiensis and other Globodera species; Heterodera avenae,Heterodera glycines, Heterodera schachtii, Heterodera trifolii, andother Heterodera species; Seed gall nematodes, Anguina species; Stem andfoliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimuslongicaudatus and other Belonolaimus species; Pine nematodes,Bursaphelenchus xylophilus and other Bursaphelenchus species; Ringnematodes, Criconema species, Criconemella species, Criconemoidesspecies, Mesocriconema species; Stem and bulb nematodes, Ditylenchusdestructor, Ditylenchus dipsaci and other Ditylenchus species; Awlnematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchusmulticinctus and other Helicotylenchus species; Sheath and sheathoidnematodes, Hemicycliophora species and Hemicriconemoides species;Hirshmanniella species; Lance nematodes, Hoploaimus species; falserootknot nematodes, Nacobbus species; Needle nematodes, Longidoruselongatus and other Longidorus species; Pin nematodes, Paratylenchusspecies; Lesion nematodes, Pratylenchus neglectus, Pratylenchuspenetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and otherPratylenchus species; Burrowing nematodes, Radopholus similis and otherRadopholus species; Reniform nematodes, Rotylenchus robustus and otherRotylenchus species; Scutellonema species; Stubby root nematodes,Trichodorus primitivus and other Trichodorus species, Paratrichodorusspecies; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchusdubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulusspecies, Dagger nematodes, Xiphinema species and other plant parasiticnematode species.

Moreover, the crystalline modification II is especially useful for thecontrol of crop pests, in particular of the Coleoptera, Lepidoptera andAcarina orders.

Moreover, the crystalline modification II is especially useful for thecontrol of non-crop pests (household, turf, ornamental). Non-crop pestsare pests of the classes Chilopoda and Diplopoda and of the ordersIsoptera, Diptera, Blattaria (Blattodea), Dermaptera, Hemiptera,Hymenoptera, Orthoptera, Siphonaptera, Thysanura, Phthiraptera, andAcarina.

For use according to the present invention, the crystalline modificationII can be converted into the customary formulations, for examplesolutions, emulsions, suspensions, dusts, powders, pastes and granules.The use form depends on the particular intended purpose; in each case,it should ensure a fine and even distribution of the compound accordingto the invention.

The formulations are prepared in a known manner (see e.g. for reviewU.S. Pat. No. 3,060,084, EP-A 707 445 (for liquid concentrates),Browning, “Agglomeration”, Chemical Engineering, Dec. 4, 1967, 147-48,Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York,1963, pages 8-57 and et seq. WO 91/13546, U.S. Pat. No. 4,172,714, U.S.Pat. No. 4,144,050, U.S. Pat. No. 3,920,442, U.S. Pat. No. 5,180,587,U.S. Pat. No. 5,232,701, U.S. Pat. No. 5,208,030, GB 2,095,558, U.S.Pat. No. 3,299,566, Klingman, Weed Control as a Science, John Wiley andSons, Inc., New York, 1961, Hance et al., Weed Control Handbook, 8thEd., Blackwell Scientific Publications, Oxford, 1989 and Mollet, H.,Grubemann, A., Formulation technology, Wiley VCH Verlag GmbH, Weinheim(Germany), 2001, 2. D. A. Knowles, Chemistry and Technology ofAgrochemical Formulations, Kluwer Academic Publishers, Dordrecht, 1998(ISBN 0-7514-0443-8), for example by extending the active compound withauxiliaries suitable for the formulation of agrochemicals, such assolvents and/or carriers, if desired surfactants (e.g. adjuvans,emulsifiers, dispersing agents), preservatives, antifoaming agents,anti-freezing agents, for seed treatment formulations also optionallycolorants and/or binders and/or gelling agents.

Examples of suitable solvents are water, aromatic solvents (for exampleSolvesso products, xylene), paraffins (for example mineral oilfractions), alcohols (for example methanol, butanol, pentanol, benzylalcohol), ketones (for example cyclohexanone, gamma-butyrolactone),pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, fattyacid dimethylamides, fatty acids and fatty acid esters. In principle,solvent mixtures may also be used.

Examples of suitable carriers are ground natural minerals (for examplekaolins, clays, talc, chalk) and ground synthetic minerals (for examplehighly disperse silica, silicates). Suitable surfactants used are alkalimetal, alkaline earth metal and ammonium salts of lignosulfonic acid,naphthalenesulfonic acid, phenolsulfonic acid,dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates,alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fattyalcohol glycol ethers, furthermore condensates of sulfonated naphthaleneand naphthalene derivatives with formaldehyde, condensates ofnaphthalene or of naphthalenesulfonic acid with phenol and formaldehyde,polyoxyethylene octylphenol ether, ethoxylated isooctylphenol,octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenylpolyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyetheralcohols, alcohol and fatty alcohol ethylene oxide condensates,ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylatedpolyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitolesters, lignosulfite waste liquors and methylcellulose.

Substances which are suitable for the preparation of directly sprayablesolutions, emulsions, pastes or oil dispersions are mineral oilfractions of medium to high boiling point, such as kerosene or dieseloil, furthermore coal tar oils and oils of vegetable or animal origin,aliphatic, cyclic and aromatic hydrocarbons, for example toluene,xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or theirderivatives, methanol, ethanol, propanol, butanol, cyclohexanol,cyclohexanone, isophorone, highly polar solvents, for example dimethylsulfoxide, N-methylpyrrolidone or water.

Also anti-freezing agents such as glycerin, ethylene glycol, propyleneglycol and bactericides can be added to the formulation.

Suitable antifoaming agents are for example antifoaming agents based onsilicon or magnesium stearate.

Suitable preservatives are for example Dichlorophen andenzylalkoholhemiformal.

Seed Treatment formulations may additionally comprise binders andoptionally colorants.

Binders can be added to improve the adhesion of the active materials onthe seeds after treatment. Suitable binders are block copolymers EO/POsurfactants but also polyvinylalcohols, polyvinylpyrrolidones,polyacrylates, polymethacrylates, polybutenes, polyisobutylenes,polystyrene, polyethyleneamines, polyethyleneamides, polyethyleneimines(Lupasol®, Polymin®), polyethers, polyurethans, polyvinylacetate, tyloseand copolymers derived from these polymers.

Optionally, also colorants can be included in the formulation. Suitablecolorants or dyes for seed treatment formulations are Rhodamin B, C.I.Pigment Red 112, C.I. Solvent Red 1, pigment blue 15:4, pigment blue15:3, pigment blue 15:2, pigment blue 15:1, pigment blue 80, pigmentyellow 1, pigment yellow 13, pigment red 112, pigment red 48:2, pigmentred 48:1, pigment red 57:1, pigment red 53:1, pigment orange 43, pigmentorange 34, pigment orange 5, pigment green 36, pigment green 7, pigmentwhite 6, pigment brown 25, basic violet 10, basic violet 49, acid red51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10,basic red 108.

Examples of a gelling agent is carrageen (Satiagel®).

Powders, materials for spreading and dustable products can be preparedby mixing or concomitantly grinding the active substances with a solidcarrier.

Granules, for example coated granules, impregnated granules andhomogeneous granules, can be prepared by binding the active compounds tosolid carriers.

Examples of solid carriers are mineral earths such as silica gels,silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess,clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate,magnesium oxide, ground synthetic materials, fertilizers, such as, forexample, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas,and products of vegetable origin, such as cereal meal, tree bark meal,wood meal and nutshell meal, cellulose powders and other solid carriers.

In general, the formulations comprise from 0.01 to 95% by weight,preferably from 0.1 to 90% by weight, of the active compound(s). In thiscase, the active compound(s) are employed in a purity of from 90% to100% by weight, preferably 95% to 100% by weight (according to NMRspectrum).

For seed treatment purposes, the respective formulations can be diluted2-10 fold leading to concentrations in the ready to use preparations of0.01 to 60% by weight active compound by weight, preferably 0.1 to 40%by weight.

The crystalline modification II can be used as such, in the form oftheir formulations or the use forms prepared therefrom, for example inthe form of directly sprayable solutions, powders, suspensions ordispersions, emulsions, oil dispersions, pastes, dustable products,materials for spreading, or granules, by means of spraying, atomizing,dusting, spreading or pouring. The use forms depend entirely on theintended purposes; they are intended to ensure in each case the finestpossible distribution of the active compound(s) according to theinvention.

Aqueous use forms can be prepared from emulsion concentrates, pastes orwettable powders (sprayable powders, oil dispersions) by adding water.To prepare emulsions, pastes or oil dispersions, the substances, as suchor dissolved in an oil or solvent, can be homogenized in water by meansof a wetter, tackifier, dispersant or emulsifier. However, it is alsopossible to prepare concentrates composed of active substance, wetter,tackifier, dispersant or emulsifier and, if appropriate, solvent or oil,and such concentrates are suitable for dilution with water.

The active compound concentrations in the ready-to-use preparations canbe varied within relatively wide ranges. In general, they are from0.0001 to 10%, preferably from 0.01 to 1% per weight.

The active compound(s) may also be used successfully in theultra-low-volume process (ULV), it being possible to apply formulationscomprising over 95% by weight of active compound, or even to apply theactive compound without additives.

The following are examples of formulations: 1. Products for dilutionwith water for foliar applications. For seed treatment purposes, suchproducts may be applied to the seed diluted or undiluted.

A) Water-Soluble Concentrates (SL, LS)

10 parts by weight of the active compound(s) are dissolved in 90 partsby weight of water or a water-soluble solvent. As an alternative,wetters or other auxiliaries are added. The active compound(s) dissolvesupon dilution with water, whereby a formulation with 10% (w/w) of activecompound(s) is obtained.

B) Dispersible Concentrates (DC)

20 parts by weight of the active compound(s) are dissolved in 70 partsby weight of cyclohexanone with addition of 10 parts by weight of adispersant, for example polyvinylpyrrolidone. Dilution with water givesa dispersion, whereby a formulation with 20% (w/w) of active compound(s)is obtained.

C) Emulsifiable Concentrates (EC)

15 parts by weight of the active compound(s) are dissolved in 80 partsby weight of xylene with addition of calcium dodecylbenzenesulfonate andcastor oil ethoxylate (in each case 5 parts by weight). Dilution withwater gives an emulsion, whereby a formulation with 15% (w/w) of activecompound(s) is obtained.

D) Emulsions (EW, EO, ES)

25 parts by weight of the active compound(s) are dissolved in 35 partsby weight of xylene with addition of calcium dodecylbenzenesulfonate andcastor oil ethoxylate (in each case 5 parts by weight). This mixture isintroduced into 30 parts by weight of water by means of an emulsifiermachine (e.g. Ultraturrax) and made into a homogeneous emulsion.Dilution with water gives an emulsion, whereby a formulation with 25%(w/w) of active compound(s) is obtained.

E) Suspensions (SC, OD, FS)

In an agitated ball mill, 20 parts by weight of the active compound(s)are comminuted with addition of 10 parts by weight of dispersants,wetters and 70 parts by weight of water or of an organic solvent to givea fine active compound(s) suspension. Dilution with water gives a stablesuspension of the active compound(s), whereby a formulation with 20%(w/w) of active compound(s) is obtained.

F) Water-Dispersible Granules and Water-Soluble Granules (WG, SG)

50 parts by weight of the active compound(s) are ground finely withaddition of 50 parts by weight of dispersants and wetters and made aswater-dispersible or water-soluble granules by means of technicalappliances (for example extrusion, spray tower, fluidized bed). Dilutionwith water gives a stable dispersion or solution of the activecompound(s), whereby a formulation with 50% (w/w) of active compound(s)is obtained.

G) Water-Dispersible Powders and Water-Soluble Powders (WP, SP, SS, WS)

75 parts by weight of the active compound(s) are ground in arotor-stator mill with addition of 25 parts by weight of dispersants,wetters and silica gel. Dilution with water gives a stable dispersion orsolution of the active compound(s), whereby a formulation with 75% (w/w)of active compound(s) is obtained.

H) Gel-Formulation (GF) (for Seed Treatment Purposes Only)

In an agitated ball mill, 20 parts by weight of the active compound(s)are comminuted with addition of 10 parts by weight of dispersants, 1part by weight of a gelling agent/wetters and 70 parts by weight ofwater or of an organic solvent to give a fine active compound(s)suspension. Dilution with water gives a stable suspension of the activecompound(s), whereby a formulation with 20% (w/w) of active compound(s)is obtained.

2. Products to be applied undiluted for foliar applications. For seedtreatment purposes, such products may be applied to the seed diluted.

I) Dustable Powders (DP, DS)

5 parts by weight of the active compound(s) are ground finely and mixedintimately with 95 parts by weight of finely divided kaolin. This givesa dustable product having 5% (w/w) of active compound(s)

J) Granules (GR, FG, GG, MG)

0.5 part by weight of the active compound(s) is ground finely andassociated with 95.5 parts by weight of carriers, whereby a formulationwith 0.5% (w/w) of active compound(s) is obtained. Current methods areextrusion, spray-drying or the fluidized bed. This gives granules to beapplied undiluted for foliar use.

K) ULV Solutions (UL)

10 parts by weight of the active compound(s) are dissolved in 90 partsby weight of an organic solvent, for example xylene. This gives aproduct having 10% (w/w) of active compound(s), which is appliedundiluted for foliar use.

Conventional seed treatment formulations include for example flowableconcentrates FS, solutions LS, powders for dry treatment DS, waterdispersible powders for slurry treatment WS, water-soluble powders SSand emulsion ES and EC and gel formulation GF. These formulation can beapplied to the seed diluted or undiluted. Application to the seeds iscarried out before sowing, either directly on the seeds.

In a preferred embodiment a FS formulation is used for seed treatment.Typically, a FS formulation may comprise 1-800 g/l of active ingredient,1-200 g/l surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l ofbinder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent,preferably water.

The invention relates in particular to pesticidal or parasiticidalcompositions in the form of an aqueous suspension concentrate (SC). Suchsuspension concentrates comprise the crystalline modification II in afinely divided particulate form, where the particles of the crystallinemodification II are suspended in an aqueous medium. The size of theactive compound particles, i.e. the size which is not exceeded by 90% byweight of the active compound particles, is typically below 30 μm, inparticular below 20 μm. Advantageously, at least 40% by weight and inparticular at least 60% by weight of the particles in the SCs accordingto the invention have diameters below 2 μm.

In addition to the active compound, suspension concentrates typicallycomprise surfactants, and also, if appropriate, antifoam agents,thickeners, antifreeze agents, stabilizers (biocides), agents foradjusting the pH and anticaking agents.

In such SCs, the amount of active compound, i.e. the total amount of thecrystalline modification II and, if appropriate, further activecompounds is usually in the range from 10 to 70% by weight, inparticular in the range from 20 to 50% by weight, based on the totalweight of the suspension concentrate.

Preferred surfactants are anionic and nonionic surfactants. The amountof surfactants will generally be from 0.5 to 20% by weight, inparticular from 1 to 15% by weight and particularly preferably from 1 to10% by weight, based on the total weight of the SCs according to theinvention. Preferably, the surfactants comprise at least one anionicsurfactant and at least one nonionic surfactant, the ratio of anionic tononionic surfactant typically being in the range from 10:1 to 1:10.

Examples of anionic surfactants include alkylaryl sulfonates, phenylsulfonates, alkyl sulfates, alkyl sulfonates, alkyl ether sulfates,alkylaryl ether sulfates, alkyl polyglycol ether phosphates, polyarylphenyl ether phosphates, alkyl sulfosuccinates, olefin sulfonates,paraffin sulfonates, petroleum sulfonates, taurides, sarcosides, fattyacids, alkylnaphthalenesulfonic acids, naphthalenesulfonic acids,lignosulfonic acids, condensates of sulfonated naphthalenes withformaldehyde or with formaldehyde and phenol and, if appropriate, urea,and also condensates of phenolsulfonic acid, formaldehyde and urea,lignosulfite waste liquors and lignosulfonates, alkyl phosphates,alkylaryl phosphates, for example tristyryl phosphates, and alsopolycarboxylates, such as, for example, polyacrylates, maleicanhydride/olefin copolymers (for example Sokalan® CP9, BASF), includingthe alkali metal, alkaline earth metal, ammonium and amine salts of thesubstances mentioned above. Preferred anionic surfactants are thosewhich carry at least one sulfonate group, and in particular their alkalimetal and their ammonium salts.

Examples of nonionic surfactants comprise alkylphenol alkoxylates,alcohol alkoxylates, fatty amine alkoxylates, polyoxyethylene glycerolfatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fattyamide alkoxylates, fatty polydiethanolamides, lanolin ethoxylates, fattyacid polyglycol esters, isotridecyl alcohol, fatty amides,methylcellulose, fatty acid esters, alkyl polyglycosides, glycerol fattyacid esters, polyethylene glycol, polypropylene glycol, polyethyleneglycol/polypropylene glycol block copolymers, polyethylene glycol alkylethers, polypropylene glycol alkyl ethers, polyethyleneglycol/polypropylene glycol ether block copolymers (polyethyleneoxide/polypropylene oxide block copolymers) and mixtures thereof.Preferred nonionic surfactants are fatty alcohol ethoxylates, alkylpolyglycosides, glycerol fatty acid esters, castor oil alkoxylates,fatty acid alkoxylates, fatty amide alkoxylates, lanolin ethoxylates,fatty acid polyglycol esters and ethylene oxide/propylene oxide blockcopolymers and mixtures thereof.

In particular, the SCs according to the invention comprise at least onesurfactant which improves wetting of the plant parts by the aqueousapplication form (wetting agent) and at least one surfactant whichstabilizes the dispersion of the active compound particles in the SC(dispersant). The amount of wetting agent is typically in the range from0.5 to 10% by weight, in particular from 0.5 to 5% by weight andespecially from 0.5 to 3% by weight, based on the total weight of theSC. The amount of dispersant is typically from 0.5 to 10% by weight andin particular from 0.5 to 5% by weight, based on the total weight of theSC.

Preferred wetting agents are of anionic or nonionic nature and selected,for example, from naphthalenesulfonic acids including their alkalimetal, alkaline earth metal, ammonium and amine salts, furthermore fattyalcohol ethoxylates, alkyl polyglycosides, glycerol fatty acid esters,castor oil alkoxylates, fatty acid alkoxylates, fatty amide alkoxylates,fatty polydiethanolamides, lanolin ethoxylates and fatty acid polyglycolesters.

Preferred dispersants are of anionic or nonionic nature and selected,for example, from polyethylene glycol/polypropylene glycol blockcopolymers, polyethylene glycol alkyl ethers, polypropylene glycol alkylethers, polyethylene glycol/polypropylene glycol ether block copolymers,alkylaryl phosphates, for example tristyryl phosphates, lignosulfonicacids, condensates of sulfonated naphthalenes with formaldehyde or withformaldehyde and phenol and, if appropriate, urea, and also condensatesof phenolsulfonic acid, formaldehyde and urea, lignosulfite wasteliquors and lignosulfonates, polycarboxylates, such as, for example,polyacrylates, maleic anhydride/olefin copolymers (for example Sokalan®CP9, BASF), including the alkali metal, alkaline earth metal, ammoniumand amine salts of the substances mentioned above.

Viscosity-modifying additives (thickeners) suitable for the SCsaccording to the invention are in particular compounds which bestow uponthe formulation pseudoplastic flow properties, i.e. high viscosity inthe resting state and low viscosity in the agitated state. Suitable are,in principle, all compounds used for this purpose in suspensionconcentrates. Mention may be made, for example, of inorganic substances,such as bentonites or attapulgites (for example Attaclay® fromEngelhardt), and organic substances, such as polysaccharides andheteropolysaccharides, such as xanthan gum such as sold under thetrademarks Kelzan® from Kelco, Rhodopol® 23 from Rhone Poulenc orVeegum® from R.T. Vanderbilt, and preference is given to using xanthangum. Frequently, the amount of viscosity-modifying additives is from 0.1to 5% by weight, based on the total weight of the SC.

Antifoam agents suitable for the SCs according to the invention are, forexample, silicone emulsions known for this purpose (Silikon® SRE, fromWacker, or Rhodorsil® from Rhodia), long-chain alcohols, fatty acids,defoamers of the type of aqueous wax dispersions, solid defoamers(so-called Compounds), organofluorine compounds and mixtures thereof.The amount of antifoam agent is typically from 0.1 to 1% by weight,based on the total weight of the SC.

Bactericides may be added for stabilizing the suspension concentratesaccording to the invention. Suitable bactericides are those based onisothiazolones, for example Proxel® from ICI or Acticide® RS from ThorChemie or Kathon® MK from Rohm & Haas. The amount of bactericides istypically from 0.05 to 0.5% by weight, based on the total weight of theSC.

Suitable antifreeze agents are liquid polyols, for example ethyleneglycol, propylene glycol or glycerol. The amount of antifreeze agents isgenerally from 1 to 20% by weight, in particular from 5 to 10% byweight, based on the total weight of the suspension concentrate.

If appropriate, the SCs according to the invention may comprise buffersfor regulating the pH. Examples of buffers are alkali metal salts ofweak inorganic or organic acids, such as, for example, phosphoric acid,boric acid, acetic acid, propionic acid, citric acid, fumaric acid,tartaric acid, oxalic acid and succinic acid.

The invention relates in particular to pesticidal or parasiticidalcompositions in the form of water-dispersible granules (WG) or a waterdispersible powder (WP). Such formulations comprise the crystallinemodification II in a finely divided particulate form, where theparticles of the crystalline modification II are homogenized in a solidor powder form. The size of the active compound particles, i.e. the sizewhich is not exceeded by 90% by weight of the active compound particles,is typically below 30 μm, in particular below 20 μm. Advantageously, atleast 40% by weight and in particular at least 60% by weight of theparticles in the WGs or WPs according to the invention have diametersbelow 5 μm.

In addition to the active compound, water-dispersible powders and waterdispersible granules typically comprise surfactants, and also, ifappropriate, antifoam agents, fillers, binders, and anticaking agents.

In such WGs and WPs, the amount of active compound, i.e. the totalamount of the crystalline modification II and, if appropriate, furtheractive compounds is usually in the range from 10 to 90% by weight, inparticular in the range from 20 to 75% by weight, based on the totalweight of the WG/WP.

Preferred surfactants are anionic and nonionic surfactants. The amountof surfactants will generally be from 0.5 to 20% by weight, inparticular from 1 to 15% by weight and particularly preferably from 1 to10% by weight, based on the total weight of the WGs or WPs according tothe invention. Preferably, the surfactants comprise at least one anionicsurfactant and at least one nonionic surfactant, the ratio of anionic tononionic surfactant typically being in the range from 10:1 to 1:10.

Examples of anionic surfactants include alkylaryl sulfonates, phenylsulfonates, alkyl sulfates, alkyl sulfonates, alkyl ether sulfates,alkylaryl ether sulfates, alkyl polyglycol ether phosphates, polyarylphenyl ether phosphates, alkyl sulfosuccinates, olefin sulfonates,paraffin sulfonates, petroleum sulfonates, taurides, sarcosides, fattyacids, alkylnaphthalenesulfonic acids, naphthalenesulfonic acids,lignosulfonic acids, condensates of sulfonated naphthalenes withformaldehyde or with formaldehyde and phenol and, if appropriate, urea,and also condensates of phenolsulfonic acid, formaldehyde and urea,lignosulfite waste liquors and lignosulfonates, alkyl phosphates,alkylaryl phosphates, for example tristyryl phosphates, and alsopolycarboxylates, such as, for example, polyacrylates, maleicanhydride/olefin copolymers (for example Sokalan® CP9, BASF), includingthe alkali metal, alkaline earth metal, ammonium and amine salts of thesubstances mentioned above. Preferred anionic surfactants are thosewhich carry at least one sulfonate group, and in particular their alkalimetal and their ammonium salts.

Examples of nonionic surfactants comprise alkylphenol alkoxylates,alcohol alkoxylates, fatty amine alkoxylates, polyoxyethylene glycerolfatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fattyamide alkoxylates, fatty polydiethanolamides, lanolin ethoxylates, fattyacid polyglycol esters, isotridecyl alcohol, fatty amides,methylcellulose, fatty acid esters, alkyl polyglycosides, glycerol fattyacid esters, polyethylene glycol, polypropylene glycol, polyethyleneglycol/polypropylene glycol block copolymers, polyethylene glycol alkylethers, polypropylene glycol alkyl ethers, polyethyleneglycol/polypropylene glycol ether block copolymers (polyethyleneoxide/polypropylene oxide block copolymers) and mixtures thereof.Preferred nonionic surfactants are fatty alcohol ethoxylates, alkylpolyglycosides, glycerol fatty acid esters, castor oil alkoxylates,fatty acid alkoxylates, fatty amide alkoxylates, lanolin ethoxylates,fatty acid polyglycol esters and ethylene oxide/propylene oxide blockcopolymers and mixtures thereof.

In particular, the WGs or WPs according to the invention comprise atleast one surfactant which improves wetting of the formulation by theaqueous application form (wetting agent) and at least one surfactantwhich allows dispersion of the active compound particles in aqueousdilutions. The amount of wetting agent is typically in the range from0.5 to 10% by weight, in particular from 0.5 to 5% by weight andespecially from 0.5 to 3% by weight, based on the total weight of theWG/WP. The amount of dispersant is typically from 0.5 to 10% by weightand in particular from 2.0 to 8% by weight, based on the total weight ofthe WG/WP.

Preferred wetting agents are of anionic or nonionic nature and selected,for example, from naphthalenesulfonic acids including their alkalimetal, alkaline earth metal, ammonium and amine salts, furthermore fattyalcohol ethoxylates, alkyl polyglycosides, glycerol fatty acid esters,castor oil alkoxylates, fatty acid alkoxylates, fatty amide alkoxylates,fatty polydiethanolamides, lanolin ethoxylates and fatty acid polyglycolesters.

Preferred dispersants are of anionic or nonionic nature and selected,for example, from polyethylene glycol/polypropylene glycol blockcopolymers, polyethylene glycol alkyl ethers, polypropylene glycol alkylethers, polyethylene glycol/polypropylene glycol ether block copolymers,alkylaryl phosphates, for example tristyryl phosphates, sodiumphosphates, sodium lauryl sulphate, modified cellulose gum,polyvinylpyrrolidinone, lignosulfonic acids, condensates of sulfonatednaphthalenes with formaldehyde or with formaldehyde and phenol and, ifappropriate, urea, and also condensates of phenol-sulfonic acid,formaldehyde and urea, lignosulfite waste liquors and lignosulfonates,polycarboxylates, such as, for example, polyacrylates, maleicanhydride/olefin copolymers (for example Sokalan® CP9, BASF), includingthe alkali metal, alkaline earth metal, ammonium and amine salts of thesubstances mentioned above.

Antifoam agents suitable for the WGs or WPs according to the inventionare, for example, tallow soap known for this purpose (Agnique Soap L,Foamaster Soap L), long-chain alcohols, fatty acids, organofluorinecompounds and mixtures thereof. The amount of antifoam agent istypically from 0.1 to 1% by weight, based on the total weight of theWG/WP.

Fillers, binders, or additional dispersing aids suitable for the WGs andWPs according to the invention typically make up the remainder of theformulation. These typically are for example kaolin or attapulgite clay,fumed or precipitated silica, diatomaceous earth, ammonium sulphate, orcalcium silicate.

The crystalline modification II is effective through both contact andingestion.

According to a preferred embodiment of the invention, the crystallinemodification II is employed via soil application. Soil application isespecially favorable for use against ants, termites, crickets, orcockroaches.

According to another preferred embodiment of the invention, for useagainst non-crop pests such as ants, termites, wasps, flies, mosquitoes,crickets, locusts, or cockroaches the crystalline modification II isprepared into a bait preparation.

The bait can be a liquid, a solid or a semisolid preparation (e.g. agel). Solid baits can be formed into various shapes and forms suitableto the respective application e.g. granules, blocks, sticks, disks.Liquid baits can be filled into various devices to ensure properapplication, e.g. open containers, spray devices, droplet sources, orevaporation sources. Gels can be based on aqueous or oily matrices andcan be formulated to particular necessities in terms of stickiness,moisture retention or aging characteristics. The bait employed in thecomposition is a product which is sufficiently attractive to inciteinsects such as ants, termites, wasps, flies, mosquitoes, crickets etc.or cockroaches to eat it. This attractant may be chosen from feedingstimulants or para and/or sex pheromones. Suitable feeding stimulantsare chosen, for example, from animal and/or plant proteins (meat-, fish-or blood meal, insect parts, crickets powder, egg yolk), from fats andoils of animal and/or plant origin, or mono-, oligo- orpolyorganosaccharides, especially from sucrose, lactose, fructose,dextrose, glucose, starch, pectin or even molasses or honey, or fromsalts such as ammonium sulfate, ammonium carbonate or ammonium acetate.Fresh or decaying parts of fruits, crops, plants, animals, insects orspecific parts thereof can also serve as a feeding stimulant. Pheromonesare known to be more insect specific. Specific pheromones are describedin the literature and are known to those skilled in the art.

Compositions of this invention may also contain other activeingredients, for example other pesticides, insecticides, fungicides,herbicides, fertilizers such as ammonium nitrate, urea, potash, andsuperphosphate, phytotoxicants and plant growth regulators, safeners andnematicides. These additional ingredients may be used sequentially or incombination with the above-described compositions, if appropriate alsoadded only immediately prior to use (tank mix). For example, theplant(s) may be sprayed with a composition of this invention eitherbefore or after being treated with other active ingredients.

The following list of pesticidal or parasiticidal compounds which can beused together with the crystalline modification II according to theinvention is intended to illustrate the possible combinations, but notto impose any limitation:

A.1. Organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl,chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon,dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion,fenthion, isoxathion, malathion, methamidophos, methidathion,methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon,parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate,phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos,tetrachlorvinphos, terbufos, triazophos, trichlorfon;A.2. Carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl,carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl,oxamyl, pirimicarb, propoxur, thiodicarb, triazamate;A.3. Pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin,cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin,zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox,fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin,prallethrin, pyrethrin I and II, resmethrin, silafluofen,tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin,profluthrin, dimefluthrin;A.4. Growth regulators: a) chitin synthesis inhibitors: benzoylureas:chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron,hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron;buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b)ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide,azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d)lipid biosynthesis inhibitors: spirodiclofen, spiromesifen,spirotetramat;A.5. Nicotinic receptor agonists/antagonists compounds: clothianidin,dinotefuran, imidacloprid, thiamethoxam, nitenpyram, acetamiprid,thiacloprid; the thiazol compound of formula Γ¹

A.6. GABA antagonist compounds: acetoprole, endosulfan, ethiprole,fipronil, vaniliprole, pyrafluprole, pyriprole,5-Amino-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-4-trifluoromethanesulfonyl-1H-pyrazole-3-carbothioicacid amide of formula Γ²

A.7. Macrocyclic lactone insecticides: abamectin, emamectin,milbemectin, lepimectin, spinosad;A.8. METI I compounds: fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad,flufenerim;A.9. METI Hand III compounds: acequinocyl, fluacyprim, hydramethylnon;A.10. Uncoupler compounds: chlorfenapyr;A.11. Oxidative phosphorylation inhibitor compounds: cyhexatin,diafenthiuron, fenbutatin oxide, propargite;A.12. Moulting disrupter compounds: cyromazine;A.13. Mixed Function Oxidase inhibitor compounds: piperonyl butoxide;A.14. Sodium channel blocker compounds: indoxacarb, metaflumizone,A.15. Various: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl,pymetrozine, sulfur, thiocyclam, flubendiamide, cyenopyrafen,flupyrazofos, cyflumetofen, amidoflumet,the anthranilamide compounds of formula Γ³

wherein A¹ is CH₃, Cl, Br, I, X is C—H, C—Cl, C—F or N, Y′ is F, Cl, orBr, Y″ is hydrogen, F, Cl, CF₃, B¹ is hydrogen, Cl, Br, I, CN, B² is Cl,Br, CF₃, OCH₂CF₃, OCF₂H, and R^(B) is hydrogen, CH₃ or CH(CH₃)₂, and themalononitrile compounds as described in JP 2002 284608, WO 02/89579, WO02/90320, WO 02/90321, WO 04/06677, WO 04/20399, JP 2004 99597, WO05/68423, WO 05/68432, or WO 05/63694, especially the malononitrilecompoundsCF₂HCF₂CF₂CF₂CH₂C(CN)₂CH₂CH₂CF₃(2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,3-trifluoropropyl)malononitrile),CF₃(CH₂)₂C(CN)₂CH₂(CF₂)₅CF₂H(2-(2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoro-heptyl)-2-(3,3,3-trifluoro-propyl)-malononitrile),CF₃(CH₂)₂C(CN)₂(CH₂)₂C(CF₃)₂F(2-(3,4,4,4-Tetrafluoro-3-trifluoromethyl-butyl)-2-(3,3,3-trifluoro-propyl)-malononitrile),CF₃(CH₂)₂C(CN)₂(CH₂)₂(CF₂)₃CF₃(2-(3,3,4,4,5,5,6,6,6-Nonafluoro-hexyl)-2-(3,3,3-trifluoro-propyl)-malononitrile),CF₂H(CF₂)₃CH₂C(CN)₂CH₂(CF₂)₃CF₂H(2,2-Bis-(2,2,3,3,4,4,5,5-octafluoro-pentyl)-malononitrile),CF₃(CH₂)₂C(CN)₂CH₂(CF₂)₃CF₃(2-(2,2,3,3,4,4,5,5,5-Nonafluoro-pentyl)-2-(3,3,3-trifluoro-propyl)-malononitrile),CF₃(CF₂)₂CH₂C(CN)₂CH₂(CF₂)₃CF₂H(2-(2,2,3,3,4,4,4-Heptafluoro-butyl)-2-(2,2,3,3,4,4,5,5-octafluoro-pentyl)-malononitrile)and CF₃CF₂CH₂C(CN)₂CH₂(CF₂)₃CF₂H(2-(2,2,3,3,4,4,5,5-Octafluoro-pentyl)-2-(2,2,3,3,3-pentafluoro-propyl)-malononitrile).

The commercially available compounds of the group A may be found in ThePesticide Manual, 13^(th) Edition, British Crop Protection Council(2003) among other publications. Thioamides of formula Γ² and theirpreparation have been described in WO 98/28279. Lepimectin is known fromAgro Project, PJB Publications Ltd, November 2004. Benclothiaz and itspreparation have been described in EP-A1 454621. Methidathion andParaoxon and their preparation have been described in Farm ChemicalsHandbook, Volume 88, Meister Publishing Company, 2001. Acetoprole andits preparation have been described in WO 98/28277. Metaflumizone andits preparation have been described in EP-A1 462 456. Flupyrazofos hasbeen described in Pesticide Science 54, 1988, p. 237-243 and in U.S.Pat. No. 4,822,779. Pyrafluprole and its preparation have been describedin JP 2002193709 and in WO 01/00614. Pyriprole and its preparation havebeen described in WO 98/45274 and in U.S. Pat. No. 6,335,357.Amidoflumet and its preparation have been described in U.S. Pat. No.6,221,890 and in JP 21010907. Flufenerim and its preparation have beendescribed in WO 03/007717 and in WO 03/007718. Cyflumetofen and itspreparation have been described in WO 04/080180. Anthranilamides offormula Γ³ and their preparation have been described in WO 01/70671; WO02/48137; WO 03/24222, WO 03/15518, WO 04/67528; WO 04/33468; and WO05/118552. The malononitrile compoundsCF₂HCF₂CF₂CF₂CH₂C(CN)₂CH₂CH₂CF₃(2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,3-trifluoropropyl)malononitrile),CF₃(CH₂)₂C(CN)₂CH₂(CF₂)₅CF₂H(2-(2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoro-heptyl)-2-(3,3,3-trifluoro-propyl)-malononitrile),CF₃(CH₂)₂C(CN)₂(CH₂)₂C(CF₃)₂F(2-(3,4,4,4-Tetrafluoro-3-trifluoromethyl-butyl)-2-(3,3,3-trifluoro-propyl)-malononitrile),CF₃(CH₂)₂C(CN)₂(CH₂)₂(CF₂)₃CF₃(2-(3,3,4,4,5,5,6,6,6-Nonafluoro-hexyl)-2-(3,3,3-trifluoro-propyl)-malononitrile),CF₂H(CF₂)₃CH₂C(CN)₂CH₂(CF₂)₃CF₂H(2,2-Bis-(2,2,3,3,4,4,5,5-octafluoro-pentyl)-malononitrile),CF₃(CH₂)₂C(CN)₂CH₂(CF₂)₃CF₃(2-(2,2,3,3,4,4,5,5,5-Nonafluoro-pentyl)-2-(3,3,3-trifluoro-propyl)-malononitrile),CF₃(CF₂)₂CH₂C(CN)₂CH₂(CF₂)₃CF₂H(2-(2,2,3,3,4,4,4-Heptafluoro-butyl)-2-(2,2,3,3,4,4,5,5-octafluoro-pentyl)-malononitrile)and CF₃CF₂CH₂C(CN)₂CH₂(CF₂)₃CF₂H(2-(2,2,3,3,4,4,5,5-Octafluoro-pentyl)-2-(2,2,3,3,3-pentafluoro-propyl)-malononitrile)have been described in WO 05/63694.

The following list of fungicidal compounds which can be used togetherwith the crystalline modification II according to the invention isintended to illustrate the possible combinations, but not to impose anylimitation:

Preferred are the binary mixtures containing modification II as compoundI.

Preferred are the tertiary mixtures containing modification II ascompound I, a compound IIA, and a compound IIB.

Preferred are the quaternary mixtures containing modification II ascompound I, a compound IIA, and two compounds IIB1 and IIB2, resp.

Especially preferred are binary mixtures containing modification II ascompound I and a fungicidal compound IIA selected from the listcomprising azoles: cyproconazole, di-fenoconazole, epoxiconazole,fenbuconazole, fluquinconazole, flutriafol, hexaconazole, ipconazole,metconazole, propiconazole, prothioconazole, tebuconazole,tetraconazole, triadimenol, triadimefon, triticonazole, cyazofamid,imazalil, prochloraz, triflumizol, benomyl, carbendazim, thiabendazole,ethaboxam, and hymexazole.

Especially preferred are binary mixtures containing modification II ascompound I and a fungicidal compound IIA selected from the listcomprising strobilurins: azoxystrobin, dimoxystrobin, enestroburin,fluoxastrobin, kresoxim-methyl, metominostrobin, picoxystrobin,pyraclostrobin, trifloxystrobin, methyl(2-chloro-5-[1-(3-methylbenzyloxy-imino)ethyl]benzyl)carbamate, methyl(2-chloro-5-[1-(6-methylpyridin-2-ylmethoxy-imino)ethyl]benzyl)carbamate,and methyl2-(ortho-((2,5-dimethylphenyloxy-methylene)phenyl)-3-methoxyacrylate;

Especially preferred are binary mixtures containing modification II ascompound I and a fungicidal compound IIA selected from the listcomprising carboxamides: boscalid, carboxin, benalaxyl, fenhexamid,flutolanil, furametpyr, metalaxyl, mefenoxam (metalaxyl-M), ofurace,oxadixyl, oxycarboxin, penthiopyrad, thifluzamide, tiadinil,dimethomorph, fluopicolide (picobenzamid), diclocymet,N-(4′-bromobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide,N-(4′-trifluoromethylbiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide,N-(4′-chloro-3′-fluorobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide,N-(3′,4′-dichloro-4-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide,N-(3′,4′-dichloro-5-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide;3,4-dichloro-N-(2-cyanophenyl)isothiazol-5-carboxamide;N-(2′,4′-difluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-(2′,4′-dichlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-(2′,4′-difluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-(2′,4′-dichloro-biphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-(2′,5′-difluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-(2′,5′-dichlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-(2′,5′-difluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-(2′,5′-dichlorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-(3′,5′-difluoro-biphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-(3′,5′-dichlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide,N-(3′,5′-difluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-(3′,5′-dichlorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-(3′-fluorobiphenyl-2-yl)-1-methyl-3-trifluoro-methyl-1H-pyrazole-4-carboxamide,N-(3′-chlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-(3′-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide,N-(3′-chlorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-(2′-fluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-(2′-chlorobiphenyl-2-yl)-1-methyl-3-trifluoro-methyl-1H-pyrazole-4-carboxamide;N-(2′-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-(2′-chlorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-(2′-fluoro-4′-chloro-5′-methylbiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-(3′,4′,5′-trifluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-(3′,4′,5′-trifluorobiphenyl-2-yl)-1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide;N-(2′,4′,5′-trifluorobiphenyl-2-yl)-1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide;N-(3′,4′,5′-tri-fluorobiphenyl-2-yl)-3-chlorofluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-[2-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-1-methyl-3-trifluoro-methyl-1H-pyrazole-4-carboxamide;N-[2-(1,1,2,3,3,3-hexafluor-opropoxy)-phenyl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide,N-[2-(2-chloro-1,1,2-trifluoroethoxy)phenyl]-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-[2-(2-chlor-1,1,2-trifluoroethoxy)phenyl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-[2-(1,1,2,2-tetra-fluoroethoxy)phenyl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-[2-(1,1,2,2-tetrafluoro-ethoxy)phenyl]-1-methyl-3-trifluoro-methyl-1H-pyrazole-4-carboxamide;N-(4′-(trifluoro-methylthio)biphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-(4′-(trifluoromethyl-thio)biphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;and 5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxylic acid[2-(1,2-dimethyl-propyl)-phenyl]-amide.

Especially preferred are binary mixtures containing modification II ascompound I and a fungicidal compound IIA selected from the listcomprising heterocylic compounds: pyrimethanil, fenpiclonil,fludioxonil, aldimorph, dodemorph, fenpropimorph, tridemorph, iprodione,procymidone, famoxadone, fenamidone, octhilinone, probenazole,diclomezine, pyroquilon, proquinazid, tricyclazole, captafol, captan,dazomet, fenoxanil, quinoxyfen,5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,6-(3,4-dichloro-phenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,6-(4-tert-butylphenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,5-methyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,5-methyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,6-methyl-5-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,6-ethyl-5-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,5-ethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,5-ethyl-6-(3,5,5-trimethyl-hex-yl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,6-octyl-5-propyl-[1,2,4]tri-azolo[1,5-a]pyrimidine-7-ylamine,5-methoxymethyl-6-octyl-[1,2,4]tri-azolo[1,5-a]pyrimidine-7-ylamine,6-octyl-5-trifluoromethyl-[1,2,4]tri-azolo[1,5-a]pyrimidine-7-ylamine,and5-trifluoromethyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine.

Especially preferred are binary mixtures containing modification II ascompound I and a fungicidal compound IIA selected from the listcomprising carbamates: mancozeb, maneb, metam, metiram, ferbam,propineb, thiram, zineb, ziram; diethofencarb, iprovalicarb,propamocarb, and methyl3-(4-chlorophenyl)-3-(2-isopropoxycarbonyl-amino-3-methylbutyrylamino)propanoate.

Especially preferred are binary mixtures containing modification II ascompound I and a fungicidal compound IIA selected from the listcomprising: guazatine; streptomycin, validamycin A; binapacryl, dinocap,dinobuton; dithianon, isoprothiolane; fentin salts, such asfentin-acetate; edifenphos, iprobenfos, fosetyl, pyrazophos,chlorothalonil, dichlofluanid, flusulfamide, phthalide, quintozene,thiophanate-methyl, tolylfluanid; copper acetate, copper hydroxide,copper oxychloride, basic copper sulfate, sulfur; cyflufenamid,cymoxanil, dimethirimol, ethirimol, furalaxyl, metrafenone, andspiroxamine.

The active compounds IIA mentioned above, their preparation and theiraction against harmful fungi are generally known (cf:http://www.hclrss.demon.co.uk/index.html); they are commerciallyavailable. The compounds named according to IUPAC, their preparation andtheir fungicidal activity are likewise known from EP-A 12 01 648; EP-A226 917; WO 98/46608; WO 99/24413; WO 2004/049804; WO 2003/066609; WO2003/053145; WO 2003/14103; EP-A 10 35 122; EP-A 10 28 125; EP-A 71 792;EP-A 141 317; WO 2003/009687; WO 05/087771; WO 2005/087772; WO2005/087773; WO 2006/087325; WO 2006/087325; WO 2006/092428; WO2006/092428; WO 2006/087343; WO 2001/42223; WO 2005/34628; WO2005/123689; WO 2005/123690; WO 2006/120219; PCT/EP2006/064991; WO2007/017450, and EP Application No. 06123463.9

With respect to their intended use, the following tertiary andquaternary mixtures of modification II as compound I are especiallypreferred:

Table 1

Mixtures wherein compound IIA is trifloxystrobin, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 2

Mixtures wherein compound IIA is azoxystrobin, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 3

Mixtures wherein compound IIA is pyraclostrobin, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 4

Mixtures wherein compound IIA is boscalid, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 5

Mixtures wherein compound IIA is metalaxyl, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 6

Mixtures wherein compound IIA is metalaxyl-M, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 7

Mixtures wherein compound IIA is cyproconazole, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 8

Mixtures wherein compound IIA is epoxiconazole, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 9

Mixtures wherein compound IIA is fenbuconazole, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 10

Mixtures wherein compound IIA is fluquinconazole, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 11

Mixtures wherein compound IIA is flutriafol, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 12

Mixtures wherein compound IIA is ipconazole, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 13

Mixtures wherein compound IIA is metconazole, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 14

Mixtures wherein compound IIA is propiconazole, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 15

Mixtures wherein compound IIA is prothioconazole, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 16

Mixtures wherein compound IIA is tebuconazole, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 17

Mixtures wherein compound IIA is triadimenol, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 18

Mixtures wherein compound IIA is triticonazole, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 19

Mixtures wherein compound IIA is imazalil, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 20

Mixtures wherein compound IIA is prochloraz, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 21

Mixtures wherein compound IIA is carbendazim, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 22

Mixtures wherein compound IIA is thiabendazole, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 23

Mixtures wherein compound IIA is ethaboxam, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 24

Mixtures wherein compound IIA is hymexazole, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 25

Mixtures wherein compound IIA is pyrimethanil, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 26

Mixtures wherein compound IIA is fludioxonil, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 27

Mixtures wherein compound IIA is aldimorph, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 28

Mixtures wherein compound IIA is dodemorph, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 29

Mixtures wherein compound IIA is fenpropimorph, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 30

Mixtures wherein compound IIA is iprodione, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 31

Mixtures wherein compound IIA is captan, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 32

Mixtures wherein compound IIA is fenoxanil, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 33

Mixtures wherein compound IIA is probenazole, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 34

Mixtures wherein compound IIA is mancozeb, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 35

Mixtures wherein compound IIA is metiram, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 36

Mixtures wherein compound IIA is thiram, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 37

Mixtures wherein compound IIA is ziram, and the combination of compoundsIIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 38

Mixtures wherein compound IIA is guazatin, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 39

Mixtures wherein compound IIA is thiophanate-methyl, and the combinationof compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 40

Mixtures wherein compound IIA is chlorothalonil, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 41

Mixtures wherein compound IIA is metrafenone, and the combination ofcompounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

TABLE Q Mixture No. Compound IIB1 Compound IIB2 M-1 azoxystrobin — M-2azoxystrobin boscalid M-3 azoxystrobin metalaxyl M-4 azoxystrobincyproconazole M-5 azoxystrobin epoxiconazole M-6 azoxystrobinfenbuconazole M-7 azoxystrobin fluquinconazole M-8 azoxystrobinflutriafol M-9 azoxystrobin ipconazole M-10 azoxystrobin metconazoleM-11 azoxystrobin propiconazole M-12 azoxystrobin prothioconazole M-13azoxystrobin tebuconazole M-14 azoxystrobin triadimenol M-15azoxystrobin triticonazole M-16 azoxystrobin imazalil M-17 azoxystrobinprochloraz M-18 azoxystrobin carbendazim M-19 azoxystrobin thiabendazoleM-20 azoxystrobin ethaboxam M-21 azoxystrobin hymexazole M-22azoxystrobin pyrimethanil M-23 azoxystrobin fludioxonil M-24azoxystrobin aldimorph M-25 azoxystrobin dodemorph M-26 azoxystrobinfenpropimorph M-27 azoxystrobin iprodione M-28 azoxystrobin captan M-29azoxystrobin fenoxanil M-30 azoxystrobin probenazol M-31 azoxystrobinmancozeb M-32 azoxystrobin metiram M-33 azoxystrobin thiram M-34azoxystrobin ziram M-35 azoxystrobin guazatin M-36 azoxystrobinthiophanate- methyl M-37 azoxystrobin chlorothalonil M-38 azoxystrobinmetrafenone M-39 trifloxystrobin — M-40 trifloxystrobin boscalid M-41trifloxystrobin metalaxyl M-42 trifloxystrobin cyproconazole M-43trifloxystrobin epoxiconazole M-44 trifloxystrobin fenbuconazole M-45trifloxystrobin fluquinconazole M-46 trifloxystrobin flutriafol M-47trifloxystrobin ipconazole M-48 trifloxystrobin metconazole M-49trifloxystrobin propiconazole M-50 trifloxystrobin prothioconazole M-51trifloxystrobin tebuconazole M-52 trifloxystrobin triadimenol M-53trifloxystrobin triticonazole M-54 trifloxystrobin imazalil M-55trifloxystrobin prochloraz M-56 trifloxystrobin carbendazim M-57trifloxystrobin thiabendazole M-58 trifloxystrobin ethaboxam M-59trifloxystrobin hymexazole M-60 trifloxystrobin pyrimethanil M-61trifloxystrobin fludioxonil M-62 trifloxystrobin aldimorph M-63trifloxystrobin dodemorph M-64 trifloxystrobin fenpropimorph M-65trifloxystrobin iprodione M-66 trifloxystrobin captan M-67trifloxystrobin fenoxanil M-68 trifloxystrobin probenazol M-69trifloxystrobin mancozeb M-70 trifloxystrobin metiram M-71trifloxystrobin thiram M-72 trifloxystrobin ziram M-73 trifloxystrobinguazatin M-74 trifloxystrobin thiophanate- methyl M-75 trifloxystrobinchlorothalonil M-76 trifloxystrobin metrafenone M-77 orysastrobin — M-78orysastrobin boscalid M-79 orysastrobin metalaxyl M-80 orysastrobincyproconazole M-81 orysastrobin epoxiconazole M-82 orysastrobinfenbuconazole M-83 orysastrobin fluquinconazole M-84 orysastrobinflutriafol M-85 orysastrobin ipconazole M-86 orysastrobin metconazoleM-87 orysastrobin propiconazole M-88 orysastrobin prothioconazole M-89orysastrobin tebuconazole M-90 orysastrobin triadimenol M-91orysastrobin triticonazole M-92 orysastrobin imazalil M-93 orysastrobinprochloraz M-94 orysastrobin carbendazim M-95 orysastrobin thiabendazoleM-96 orysastrobin ethaboxam M-97 orysastrobin hymexazole M-98orysastrobin pyrimethanil M-99 orysastrobin fludioxonil M-100orysastrobin aldimorph M-101 orysastrobin dodemorph M-102 orysastrobinfenpropimorph M-103 orysastrobin iprodione M-104 orysastrobin captanM-105 orysastrobin fenoxanil M-106 orysastrobin probenazol M-107orysastrobin mancozeb M-108 orysastrobin metiram M-109 orysastrobinthiram M-110 orysastrobin ziram M-111 orysastrobin guazatin M-112orysastrobin thiophanate- methyl M-113 orysastrobin chlorothalonil M-114orysastrobin metrafenone M-115 pyraclostrobin — M-116 pyraclostrobinboscalid M-117 pyraclostrobin metalaxyl M-118 pyraclostrobincyproconazole M-119 pyraclostrobin epoxiconazole M-120 pyraclostrobinfenbuconazole M-121 pyraclostrobin fluquinconazole M-122 pyraclostrobinflutriafol M-123 pyraclostrobin ipconazole M-124 pyraclostrobinmetconazole M-125 pyraclostrobin propiconazole M-126 pyraclostrobinprothioconazole M-127 pyraclostrobin tebuconazole M-128 pyraclostrobintriadimenol M-129 pyraclostrobin triticonazole M-130 pyraclostrobinimazalil M-131 pyraclostrobin prochloraz M-132 pyraclostrobincarbendazim M-133 pyraclostrobin thiabendazole M-134 pyraclostrobinethaboxam M-135 pyraclostrobin hymexazole M-136 pyraclostrobinpyrimethanil M-137 pyraclostrobin fludioxonil M-138 pyraclostrobinaldimorph M-139 pyraclostrobin dodemorph M-140 pyraclostrobinfenpropimorph M-141 pyraclostrobin iprodione M-142 pyraclostrobin captanM-143 pyraclostrobin fenoxanil M-144 pyraclostrobin probenazol M-145pyraclostrobin mancozeb M-146 pyraclostrobin metiram M-147pyraclostrobin thiram M-148 pyraclostrobin ziram M-149 pyraclostrobinguazatin M-150 pyraclostrobin thiophanate- methyl M-151 pyraclostrobinchlorothalonil M-152 pyraclostrobin metrafenone M-153 boscalid — M-154boscalid metalaxyl M-155 boscalid cyproconazole M-156 boscalidepoxiconazole M-157 boscalid fenbuconazole M-158 boscalidfluquinconazole M-159 boscalid flutriafol M-160 boscalid ipconazoleM-161 boscalid metconazole M-162 boscalid propiconazole M-163 boscalidprothioconazole M-164 boscalid tebuconazole M-165 boscalid triadimenolM-166 boscalid triticonazole M-167 boscalid imazalil M-168 boscalidprochloraz M-169 boscalid carbendazim M-170 boscalid thiabendazole M-171boscalid ethaboxam M-172 boscalid hymexazole M-173 boscalid pyrimethanilM-174 boscalid fludioxonil M-175 boscalid aldimorph M-176 boscaliddodemorph M-177 boscalid fenpropimorph M-178 boscalid iprodione M-179boscalid captan M-180 boscalid fenoxanil M-181 boscalid probenazol M-182boscalid mancozeb M-183 boscalid metiram M-184 boscalid thiram M-185boscalid ziram M-186 boscalid guazatin M-187 boscalid thiophanate-methyl M-188 boscalid chlorothalonil M-189 boscalid metrafenone M-190metalaxyl — M-191 metalaxyl cyproconazole M-192 metalaxyl epoxiconazoleM-193 metalaxyl fenbuconazole M-194 metalaxyl fluquinconazole M-195metalaxyl flutriafol M-196 metalaxyl ipconazole M-197 metalaxylmetconazole M-198 metalaxyl propiconazole M-199 metalaxylprothioconazole M-200 metalaxyl tebuconazole M-201 metalaxyl triadimenolM-202 metalaxyl triticonazole M-203 metalaxyl imazalil M-204 metalaxylprochloraz M-205 metalaxyl carbendazim M-206 metalaxyl thiabendazoleM-207 metalaxyl ethaboxam M-208 metalaxyl hymexazole M-209 metalaxylpyrimethanil M-210 metalaxyl fludioxonil M-211 metalaxyl aldimorph M-212metalaxyl dodemorph M-213 metalaxyl fenpropimorph M-214 metalaxyliprodione M-215 metalaxyl captan M-216 metalaxyl fenoxanil M-217metalaxyl probenazol M-218 metalaxyl mancozeb M-219 metalaxyl metiramM-220 metalaxyl thiram M-221 metalaxyl ziram M-222 metalaxyl guazatinM-223 metalaxyl thiophanate- methyl M-224 metalaxyl chlorothalonil M-225metalaxyl metrafenone M-226 cyproconazole — M-227 cyproconazoleepoxiconazole M-228 cyproconazole fenbuconazole M-229 cyproconazolefluquinconazole M-230 cyproconazole flutriafol M-231 cyproconazoleipconazole M-232 cyproconazole metconazole M-233 cyproconazolepropiconazole M-234 cyproconazole prothioconazole M-235 cyproconazoletebuconazole M-236 cyproconazole triadimenol M-237 cyproconazoletriticonazole M-238 cyproconazole imazalil M-239 cyproconazoleprochloraz M-240 cyproconazole carbendazim M-241 cyproconazolethiabendazole M-242 cyproconazole ethaboxam M-243 cyproconazolehymexazole M-244 cyproconazole pyrimethanil M-245 cyproconazolefludioxonil M-246 cyproconazole aldimorph M-247 cyproconazole dodemorphM-248 cyproconazole fenpropimorph M-249 cyproconazole iprodione M-250cyproconazole captan M-251 cyproconazole fenoxanil M-252 cyproconazoleprobenazol M-253 cyproconazole mancozeb M-254 cyproconazole metiramM-255 cyproconazole thiram M-256 cyproconazole ziram M-257 cyproconazoleguazatin M-258 cyproconazole thiophanate- methyl M-259 cyproconazolechlorothalonil M-260 cyproconazole metrafenone M-261 epoxiconazole —M-262 epoxiconazole fenbuconazole M-263 epoxiconazole fluquinconazoleM-264 epoxiconazole flutriafol M-265 epoxiconazole ipconazole M-266epoxiconazole metconazole M-267 epoxiconazole propiconazole M-268epoxiconazole prothioconazole M-269 epoxiconazole tebuconazole M-270epoxiconazole triadimenol M-271 epoxiconazole triticonazole M-272epoxiconazole imazalil M-273 epoxiconazole prochloraz M-274epoxiconazole carbendazim M-275 epoxiconazole thiabendazole M-276epoxiconazole ethaboxam M-277 epoxiconazole hymexazole M-278epoxiconazole pyrimethanil M-279 epoxiconazole fludioxonil M-280epoxiconazole aldimorph M-281 epoxiconazole dodemorph M-282epoxiconazole fenpropimorph M-283 epoxiconazole iprodione M-284epoxiconazole captan M-285 epoxiconazole fenoxanil M-286 epoxiconazoleprobenazol M-287 epoxiconazole mancozeb M-288 epoxiconazole metiramM-289 epoxiconazole thiram M-290 epoxiconazole ziram M-291 epoxiconazoleguazatin M-292 epoxiconazole thiophanate- methyl M-293 epoxiconazolechlorothalonil M-294 epoxiconazole metrafenone M-295 fenbuconazole —M-296 fenbuconazole fluquinconazole M-297 fenbuconazole flutriafol M-298fenbuconazole ipconazole M-299 fenbuconazole metconazole M-300fenbuconazole propiconazole M-301 fenbuconazole prothioconazole M-302fenbuconazole tebuconazole M-303 fenbuconazole triadimenol M-304fenbuconazole triticonazole M-305 fenbuconazole imazalil M-306fenbuconazole prochloraz M-307 fenbuconazole carbendazim M-308fenbuconazole thiabendazole M-309 fenbuconazole ethaboxam M-310fenbuconazole hymexazole M-311 fenbuconazole pyrimethanil M-312fenbuconazole fludioxonil M-313 fenbuconazole aldimorph M-314fenbuconazole dodemorph M-315 fenbuconazole fenpropimorph M-316fenbuconazole iprodione M-317 fenbuconazole captan M-318 fenbuconazolefenoxanil M-319 fenbuconazole probenazol M-320 fenbuconazole mancozebM-321 fenbuconazole metiram M-322 fenbuconazole thiram M-323fenbuconazole ziram M-324 fenbuconazole guazatin M-325 fenbuconazolethiophanate- methyl M-326 fenbuconazole chlorothalonil M-327fenbuconazole metrafenone M-328 fluquinconazole — M-329 fluquinconazoleflutriafol M-330 fluquinconazole ipconazole M-331 fluquinconazolemetconazole M-332 fluquinconazole propiconazole M-333 fluquinconazoleprothioconazole M-334 fluquinconazole tebuconazole M-335 fluquinconazoletriadimenol M-336 fluquinconazole triticonazole M-337 fluquinconazoleimazalil M-338 fluquinconazole prochloraz M-339 fluquinconazolecarbendazim M-340 fluquinconazole thiabendazole M-341 fluquinconazoleethaboxam M-342 fluquinconazole hymexazole M-343 fluquinconazolepyrimethanil M-344 fluquinconazole fludioxonil M-345 fluquinconazolealdimorph M-346 fluquinconazole dodemorph M-347 fluquinconazolefenpropimorph M-348 fluquinconazole iprodione M-349 fluquinconazolecaptan M-350 fluquinconazole fenoxanil M-351 fluquinconazole probenazolM-352 fluquinconazole mancozeb M-353 fluquinconazole metiram M-354fluquinconazole thiram M-355 fluquinconazole ziram M-356 fluquinconazoleguazatin M-357 fluquinconazole thiophanate- methyl M-358 fluquinconazolechlorothalonil M-359 fluquinconazole metrafenone M-360 flutriafol —M-361 flutriafol ipconazole M-362 flutriafol metconazole M-363flutriafol propiconazole M-364 flutriafol prothioconazole M-365flutriafol tebuconazole M-366 flutriafol triadimenol M-367 flutriafoltriticonazole M-368 flutriafol imazalil M-369 flutriafol prochlorazM-370 flutriafol carbendazim M-371 flutriafol thiabendazole M-372flutriafol ethaboxam M-373 flutriafol hymexazole M-374 flutriafolpyrimethanil M-375 flutriafol fludioxonil M-376 flutriafol aldimorphM-377 flutriafol dodemorph M-378 flutriafol fenpropimorph M-379flutriafol iprodione M-380 flutriafol captan M-381 flutriafol fenoxanilM-382 flutriafol probenazol M-383 flutriafol mancozeb M-384 flutriafolmetiram M-385 flutriafol thiram M-386 flutriafol ziram M-387 flutriafolguazatin M-388 flutriafol thiophanate- methyl M-389 flutriafolchlorothalonil M-390 flutriafol metrafenone M-391 ipconazole — M-392ipconazole metconazole M-393 ipconazole propiconazole M-394 ipconazoleprothioconazole M-395 ipconazole tebuconazole M-396 ipconazoletriadimenol M-397 ipconazole triticonazole M-398 ipconazole imazalilM-399 ipconazole prochloraz M-400 ipconazole carbendazim M-401ipconazole thiabendazole M-402 ipconazole ethaboxam M-403 ipconazolehymexazole M-404 ipconazole pyrimethanil M-405 ipconazole fludioxonilM-406 ipconazole aldimorph M-407 ipconazole dodemorph M-408 ipconazolefenpropimorph M-409 ipconazole iprodione M-410 ipconazole captan M-411ipconazole fenoxanil M-412 ipconazole probenazol M-413 ipconazolemancozeb M-414 ipconazole metiram M-415 ipconazole thiram M-416ipconazole ziram M-417 ipconazole guazatin M-418 ipconazole thiophanate-methyl M-419 ipconazole chlorothalonil M-420 ipconazole metrafenoneM-421 metconazole — M-422 metconazole propiconazole M-423 metconazoleprothioconazole M-424 metconazole tebuconazole M-425 metconazoletriadimenol M-426 metconazole triticonazole M-427 metconazole imazalilM-428 metconazole prochloraz M-429 metconazole carbendazim M-430metconazole thiabendazole M-431 metconazole ethaboxam M-432 metconazolehymexazole M-433 metconazole pyrimethanil M-434 metconazole fludioxonilM-435 metconazole aldimorph M-436 metconazole dodemorph M-437metconazole fenpropimorph M-438 metconazole iprodione M-439 metconazolecaptan M-440 metconazole fenoxanil M-441 metconazole probenazol M-442metconazole mancozeb M-443 metconazole metiram M-444 metconazole thiramM-445 metconazole ziram M-446 metconazole guazatin M-447 metconazolethiophanate- methyl M-448 metconazole chlorothalonil M-449 metconazolemetrafenone M-450 propiconazole — M-451 propiconazole prothioconazoleM-452 propiconazole tebuconazole M-453 propiconazole triadimenol M-454propiconazole triticonazole M-455 propiconazole imazalil M-456propiconazole prochloraz M-457 propiconazole carbendazim M-458propiconazole thiabendazole M-459 propiconazole ethaboxam M-460propiconazole hymexazole M-461 propiconazole pyrimethanil M-462propiconazole fludioxonil M-463 propiconazole aldimorph M-464propiconazole dodemorph M-465 propiconazole fenpropimorph M-466propiconazole iprodione M-467 propiconazole captan M-468 propiconazolefenoxanil M-469 propiconazole probenazol M-470 propiconazole mancozebM-471 propiconazole metiram M-472 propiconazole thiram M-473propiconazole ziram M-474 propiconazole guazatin M-475 propiconazolethiophanate- methyl M-476 propiconazole chlorothalonil M-477propiconazole metrafenone M-478 prothioconazole — M-479 prothioconazoletebuconazole M-480 prothioconazole triadimenol M-481 prothioconazoletriticonazole M-482 prothioconazole imazalil M-483 prothioconazoleprochloraz M-484 prothioconazole carbendazim M-485 prothioconazolethiabendazole M-486 prothioconazole ethaboxam M-487 prothioconazolehymexazole M-488 prothioconazole pyrimethanil M-489 prothioconazolefludioxonil M-490 prothioconazole aldimorph M-491 prothioconazoledodemorph M-492 prothioconazole fenpropimorph M-493 prothioconazoleiprodione M-494 prothioconazole captan M-495 prothioconazole fenoxanilM-496 prothioconazole probenazol M-497 prothioconazole mancozeb M-498prothioconazole metiram M-499 prothioconazole thiram M-500prothioconazole ziram M-501 prothioconazole guazatin M-502prothioconazole thiophanate- methyl M-503 prothioconazole chlorothalonilM-504 prothioconazole metrafenone M-505 tebuconazole — M-506tebuconazole triadimenol M-507 tebuconazole triticonazole M-508tebuconazole imazalil M-509 tebuconazole prochloraz M-510 tebuconazolecarbendazim M-511 tebuconazole thiabendazole M-512 tebuconazoleethaboxam M-513 tebuconazole hymexazole M-514 tebuconazole pyrimethanilM-515 tebuconazole fludioxonil M-516 tebuconazole aldimorph M-517tebuconazole dodemorph M-518 tebuconazole fenpropimorph M-519tebuconazole iprodione M-520 tebuconazole captan M-521 tebuconazolefenoxanil M-522 tebuconazole probenazol M-523 tebuconazole mancozebM-524 tebuconazole metiram M-525 tebuconazole thiram M-526 tebuconazoleziram M-527 tebuconazole guazatin M-528 tebuconazole thiophanate- methylM-529 tebuconazole chlorothalonil M-530 tebuconazole metrafenone M-531triadimenol — M-532 triadimenol triticonazole M-533 triadimenol imazalilM-534 triadimenol prochloraz M-535 triadimenol carbendazim M-536triadimenol thiabendazole M-537 triadimenol ethaboxam M-538 triadimenolhymexazole M-539 triadimenol pyrimethanil M-540 triadimenol fludioxonilM-541 triadimenol aldimorph M-542 triadimenol dodemorph M-543triadimenol fenpropimorph M-544 triadimenol iprodione M-545 triadimenolcaptan M-546 triadimenol fenoxanil M-547 triadimenol probenazol M-548triadimenol mancozeb M-549 triadimenol metiram M-550 triadimenol thiramM-551 triadimenol ziram M-552 triadimenol guazatin M-553 triadimenolthiophanate- methyl M-554 triadimenol chlorothalonil M-555 triadimenolmetrafenone M-556 triticonazole — M-557 triticonazole imazalil M-558triticonazole prochloraz M-559 triticonazole carbendazim M-560triticonazole thiabendazole M-561 triticonazole ethaboxam M-562triticonazole hymexazole M-563 triticonazole pyrimethanil M-564triticonazole fludioxonil M-565 triticonazole aldimorph M-566triticonazole dodemorph M-567 triticonazole fenpropimorph M-568triticonazole iprodione M-569 triticonazole captan M-570 triticonazolefenoxanil M-571 triticonazole probenazol M-572 triticonazole mancozebM-573 triticonazole metiram M-574 triticonazole thiram M-575triticonazole ziram M-576 triticonazole guazatin M-577 triticonazolethiophanate- methyl M-578 triticonazole chlorothalonil M-579triticonazole metrafenone M-580 imazalil — M-581 imazalil prochlorazM-582 imazalil carbendazim M-583 imazalil thiabendazole M-584 imazalilethaboxam M-585 imazalil hymexazole M-586 imazalil pyrimethanil M-587imazalil fludioxonil M-588 imazalil aldimorph M-589 imazalil dodemorphM-590 imazalil fenpropimorph M-591 imazalil iprodione M-592 imazalilcaptan M-593 imazalil fenoxanil M-594 imazalil probenazol M-595 imazalilmancozeb M-596 imazalil metiram M-597 imazalil thiram M-598 imazalilziram M-599 imazalil guazatin M-600 imazalil thiophanate- methyl M-601imazalil chlorothalonil M-602 imazalil metrafenone M-603 prochloraz —M-604 prochloraz carbendazim M-605 prochloraz thiabendazole M-606prochloraz ethaboxam M-607 prochloraz hymexazole M-608 prochlorazpyrimethanil M-609 prochloraz fludioxonil M-610 prochloraz aldimorphM-611 prochloraz dodemorph M-612 prochloraz fenpropimorph M-613prochloraz iprodione M-614 prochloraz captan M-615 prochloraz fenoxanilM-616 prochloraz probenazol M-617 prochloraz mancozeb M-618 prochlorazmetiram M-619 prochloraz thiram M-620 prochloraz ziram M-621 prochlorazguazatin M-622 prochloraz thiophanate- methyl M-623 prochlorazchlorothalonil M-624 prochloraz metrafenone M-625 carbendazim — M-626carbendazim thiabendazole M-627 carbendazim ethaboxam M-628 carbendazimhymexazole M-629 carbendazim pyrimethanil M-630 carbendazim fludioxonilM-631 carbendazim aldimorph M-632 carbendazim dodemorph M-633carbendazim fenpropimorph M-634 carbendazim iprodione M-635 carbendazimcaptan M-636 carbendazim fenoxanil M-637 carbendazim probenazol M-638carbendazim mancozeb M-639 carbendazim metiram M-640 carbendazim thiramM-641 carbendazim ziram M-642 carbendazim guazatin M-643 carbendazimthiophanate- methyl M-644 carbendazim chlorothalonil M-645 carbendazimmetrafenone M-646 thiabendazole — M-647 thiabendazole ethaboxam M-648thiabendazole hymexazole M-649 thiabendazole pyrimethanil M-650thiabendazole fludioxonil M-651 thiabendazole aldimorph M-652thiabendazole dodemorph M-653 thiabendazole fenpropimorph M-654thiabendazole iprodione M-655 thiabendazole captan M-656 thiabendazolefenoxanil M-657 thiabendazole probenazol M-658 thiabendazole mancozebM-659 thiabendazole metiram M-660 thiabendazole thiram M-661thiabendazole ziram M-662 thiabendazole guazatin M-663 thiabendazolethiophanate- methyl M-664 thiabendazole chlorothalonil M-665thiabendazole metrafenone M-666 ethaboxam — M-667 ethaboxam hymexazoleM-668 ethaboxam pyrimethanil M-669 ethaboxam fludioxonil M-670 ethaboxamaldimorph M-671 ethaboxam dodemorph M-672 ethaboxam fenpropimorph M-673ethaboxam iprodione M-674 ethaboxam captan M-675 ethaboxam fenoxanilM-676 ethaboxam probenazol M-677 ethaboxam mancozeb M-678 ethaboxammetiram M-679 ethaboxam thiram M-680 ethaboxam ziram M-681 ethaboxamguazatin M-682 ethaboxam thiophanate- methyl M-683 ethaboxamchlorothalonil M-684 ethaboxam metrafenone M-685 hymexazole — M-686hymexazole pyrimethanil M-687 hymexazole fludioxonil M-688 hymexazolealdimorph M-689 hymexazole dodemorph M-690 hymexazole fenpropimorphM-691 hymexazole iprodione M-692 hymexazole captan M-693 hymexazolefenoxanil M-694 hymexazole probenazol M-695 hymexazole mancozeb M-696hymexazole metiram M-697 hymexazole thiram M-698 hymexazole ziram M-699hymexazole guazatin M-700 hymexazole thiophanate- methyl M-701hymexazole chlorothalonil M-702 hymexazole metrafenone M-703pyrimethanil — M-704 pyrimethanil fludioxonil M-705 pyrimethanilaldimorph M-706 pyrimethanil dodemorph M-707 pyrimethanil fenpropimorphM-708 pyrimethanil iprodione M-709 pyrimethanil captan M-710pyrimethanil fenoxanil M-711 pyrimethanil probenazol M-712 pyrimethanilmancozeb M-713 pyrimethanil metiram M-714 pyrimethanil thiram M-715pyrimethanil ziram M-716 pyrimethanil guazatin M-717 pyrimethanilthiophanate- methyl M-718 pyrimethanil chlorothalonil M-719 pyrimethanilmetrafenone M-720 fludioxonil — M-721 fludioxonil aldimorph M-722fludioxonil dodemorph M-723 fludioxonil fenpropimorph M-724 fludioxoniliprodione M-725 fludioxonil captan M-726 fludioxonil fenoxanil M-727fludioxonil probenazol M-728 fludioxonil mancozeb M-729 fludioxonilmetiram M-730 fludioxonil thiram M-731 fludioxonil ziram M-732fludioxonil guazatin M-733 fludioxonil thiophanate- methyl M-734fludioxonil chlorothalonil M-735 fludioxonil metrafenone M-736 aldimorph— M-737 aldimorph dodemorph M-738 aldimorph fenpropimorph M-739aldimorph iprodione M-740 aldimorph captan M-741 aldimorph fenoxanilM-742 aldimorph probenazol M-743 aldimorph mancozeb M-744 aldimorphmetiram M-745 aldimorph thiram M-746 aldimorph ziram M-747 aldimorphguazatin M-748 aldimorph thiophanate- methyl M-749 aldimorphchlorothalonil M-750 aldimorph metrafenone M-751 dodemorph — M-752dodemorph fenpropimorph M-753 dodemorph iprodione M-754 dodemorph captanM-755 dodemorph fenoxanil M-756 dodemorph probenazol M-757 dodemorphmancozeb M-758 dodemorph metiram M-759 dodemorph thiram M-760 dodemorphziram M-761 dodemorph guazatin M-762 dodemorph thiophanate- methyl M-763dodemorph chlorothalonil M-764 dodemorph metrafenone M-765 fenpropimorph— M-766 fenpropimorph iprodione M-767 fenpropimorph captan M-768fenpropimorph fenoxanil M-769 fenpropimorph probenazol M-770fenpropimorph mancozeb M-771 fenpropimorph metiram M-772 fenpropimorphthiram M-773 fenpropimorph ziram M-774 fenpropimorph guazatin M-775fenpropimorph thiophanate- methyl M-776 fenpropimorph chlorothalonilM-777 fenpropimorph metrafenone M-778 iprodione — M-779 iprodione captanM-780 iprodione fenoxanil M-781 iprodione probenazol M-782 iprodionemancozeb M-783 iprodione metiram M-784 iprodione thiram M-785 iprodioneziram M-786 iprodione guazatin M-787 iprodione thiophanate- methyl M-788iprodione chlorothalonil M-789 iprodione metrafenone M-790 captan —M-791 captan fenoxanil M-792 captan probenazol M-793 captan mancozebM-794 captan metiram M-795 captan thiram M-796 captan ziram M-797 captanguazatin M-798 captan thiophanate- methyl M-799 captan chlorothalonilM-800 captan metrafenone M-801 fenoxanil — M-802 fenoxanil probenazolM-803 fenoxanil mancozeb M-804 fenoxanil metiram M-805 fenoxanil thiramM-806 fenoxanil ziram M-807 fenoxanil guazatin M-808 fenoxanilthiophanate- methyl M-809 fenoxanil chlorothalonil M-810 fenoxanilmetrafenone M-811 probenazol — M-812 probenazol mancozeb M-813probenazol metiram M-814 probenazol thiram M-815 probenazol ziram M-816probenazol guazatin M-817 probenazol thiophanate- methyl M-818probenazol chlorothalonil M-819 probenazol metrafenone M-820 mancozeb —M-821 mancozeb metiram M-822 mancozeb thiram M-823 mancozeb ziram M-824mancozeb guazatin M-825 mancozeb thiophanate- methyl M-826 mancozebchlorothalonil M-827 mancozeb metrafenone M-828 metiram — M-829 metiramthiram M-830 metiram ziram M-831 metiram guazatin M-832 metiramthiophanate- methyl M-833 metiram chlorothalonil M-834 metirammetrafenone M-835 thiram — M-836 thiram ziram M-837 thiram guazatinM-838 thiram thiophanate- methyl M-839 thiram chlorothalonil M-840thiram metrafenone M-841 ziram — M-842 ziram guazatin M-843 ziramthiophanate- methyl M-844 ziram chlorothalonil M-845 ziram metrafenoneM-846 guazatin — M-847 guazatin thiophanate- methyl M-848 guazatinchlorothalonil M-849 guazatin metrafenone M-850 thiophanate- — methylM-851 thiophanate- chlorothalonil methyl M-852 thiophanate- metrafenonemethyl M-853 chlorothalonil — M-854 chlorothalonil metrafenone M-855metrafenone —

The crystalline modification II and the one or more compound(s) ofgroups A.1-A.15 are usually applied in a weight ratio of from 500:1 to1:100, preferably from 20:1 to 1:50, in particular from 5:1 to 1:20.

The afore-mentioned applies also to the ratios of combinations ofmodification II with fungicidal compounds IIA. Compounds IIB are usuallycombined with modification II in ratios from 100:1 to 1:100.

Depending on the desired effect, the application rates of the mixturesaccording to the invention are from 5 g/ha to 2000 g/ha, preferably from50 to 1500 g/ha, in particular from 50 to 750 g/ha.

The crystalline modification II, the mixtures and the compositionsaccording to the invention can be applied to any and all developmentalstages, such as egg, larva, pupa, and adult. The pests may be controlledby contacting the target pest, its food supply, habitat, breeding groundor its locus with a pesticidally effective amount of the crystallinemodification II, the mixtures or the compositions according to theinvention.

“Locus” means a plant, seed, soil, area, material or environment inwhich a pest is growing or may grow.

In general, “pesticidally effective amount” means the amount of thecrystalline modification II, the mixtures and the compositions accordingto the invention needed to achieve an observable effect on growth,including the effects of necrosis, death, retardation, prevention, andremoval, destruction, or otherwise diminishing the occurrence andactivity of the target organism. The pesticidally effective amount canvary for the various mixtures/compositions used in the invention. Apesticidally effective amount of the mixtures/compositions will alsovary according to the prevailing conditions such as desired pesticidaleffect and duration, weather, target species, locus, mode ofapplication, and the like.

The crystalline modification II, the mixtures and the compositionsaccording to the invention can also be employed for protecting plantsfrom attack or infestation by insects, acarids or nematodes comprisingcontacting a plant, or soil or water in which the plant is growing.

In the context of the present invention, the term plant refers to anentire plant, a part of the plant or the propagation material of theplant, that is, the seed or the seedling.

Plants which can be treated with the crystalline modification II, themixtures and the compositions according to the invention include allgenetically modified plants or transgenic plants, e.g. crops whichtolerate the action of herbicides or fungicides or insecticides owing tobreeding, including genetic engineering methods, or plants which havemodified characteristics in comparison with existing plants, which canbe generated for example by traditional breeding methods and/or thegeneration of mutants, or by recombinant procedures.

Some of the inventive mixtures and compositions have systemic action andcan therefore be used for the protection of the plant shoot againstfoliar pests as well as for the treatment of the seed and roots againstsoil pests. The term seed treatment comprises all suitable seedtreatment techniques known in the art, such as, but not limited to, seeddressing, seed coating, seed dusting, seed soaking, seed film coating,seed multilayer coating, seed encrusting, seed dripping, and seedpelleting.

The present invention also comprises seeds coated with or containing thecrystalline modification II or the mixtures or the compositionsaccording to the invention.

The term seed embraces seeds and plant propagules of all kinds includingbut not limited to true seeds, seed pieces, suckers, corms, bulbs,fruit, tubers, grains, cuttings, cut shoots and the like and means in apreferred embodiment true seeds.

Suitable seed is seed of cereals, root crops, oil crops, vegetables,spices, ornamentals, for example seed of durum and other wheat, barley,oats, rye, maize (fodder maize and sugar maize/sweet and field corn),soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice,oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes,grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash,cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species,melons, beans, peas, garlic, onions, carrots, tuberous plants such aspotatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums,pansies and impatiens.

In addition, the crystalline modification II, the mixtures and thecompositions according to the invention may also be used for thetreatment seeds from plants, which tolerate the action of herbicides orfungicides or insecticides or nematicides owing to breeding, mutationand/or genetic engineering methods.

For example, the crystalline modification II, the mixtures and thecompositions according to the invention can be employed in transgeniccrops which are resistant to herbicides from the group consisting of thesulfonylureas (EP-A-0257993, U.S. Pat. No. 5,013,659), imidazolinones(see for example U.S. Pat. No. 6,222,100, WO0182685, WO0026390,WO9741218, WO9802526, WO9802527, WO 04/106529, WO 05/20673, WO 03/14357,WO 03/13225, WO 03/14356, WO 04/16073), glufosinate-type (see forexample EP-A-0242236, EP-A-242246) or glyphosate-type (see for exampleWO 92/00377) or in plants resistant towards herbicides selected from thegroup of cyclohexadienone/aryloxyphenoxypropionic acid herbicides (U.S.Pat. No. 5,162,602, U.S. Pat. No. 5,290,696, U.S. Pat. No. 5,498,544,U.S. Pat. No. 5,428,001, U.S. Pat. No. 6,069,298, U.S. Pat. No.6,268,550, U.S. Pat. No. 6,146,867, U.S. Pat. No. 6,222,099, U.S. Pat.No. 6,414,222) or in transgenic crop plants, for example cotton, withthe capability of producing Bacillus thuringiensis toxins (Bt toxins)which make the plants resistant to certain pests (EP-A-0142924,EP-A-0193259).

Furthermore, the crystalline modification II, the mixtures and thecompositions according to the invention can be used also for thetreatment of seeds from plants, which have modified characteristics incomparison with existing plants consist, which can be generated, forexample by traditional breeding methods and/or the generation ofmutants, or by recombinant procedures). For example, a number of caseshave been described of recombinant modifications of crop plants for thepurpose of modifying the starch synthesized in the plants (e.g. WO92/11376, WO 92/14827, WO 91/19806) or of transgenic crop plants havinga modified fatty acid composition (WO 91/13972).

The seed treatment application of the crystalline modification II, themixtures and the compositions according to the invention is carried outby spraying or dusting the seeds before sowing of the plants and beforeemergence of the plants.

In the treatment of seeds the corresponding formulations are applied bytreating the seeds with an effective amount of the crystallinemodification II, the mixtures or the compositions according to theinvention. Herein, the application rates of the crystalline modificationII are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from1 g to 5 kg per 100 kg of seed, in particular from 1 g to 2.5 kg per 100kg of seed. For specific crops such as lettuce and onions the rates canbe higher.

The mixtures and the compositions according to the invention areeffective through both contact (via soil, glass, wall, bed net, carpet,plant parts or animal parts), and ingestion (bait, or plant part) andthrough trophallaxis and transfer.

Preferred application methods are into water bodies, via soil, cracksand crevices, pastures, manure piles, sewers, into water, on floor,wall, or by perimeter spray application and bait.

According to another preferred embodiment of the invention, for useagainst non-crop pests such as ants, termites, wasps, flies, mosquitoes,crickets, locusts, or cockroaches the mixtures and the compositionsaccording to the invention are prepared into a bait preparation.

The bait can be a liquid, a solid or a semisolid preparation (e.g. agel). The bait employed in the mixtures/compositions is a product whichis sufficiently attractive to incite insects such as ants, termites,wasps, flies, mosquitoes, crickets etc. or cockroaches to eat it. Thisattractant may be chosen from feeding stimulants or para and/or sexpheromones readily known in the art.

Methods to control infectious diseases transmitted by insects (e.g.malaria, dengue and yellow fever, lymphatic filariasis, andleishmaniasis) with the inventive mixtures and their respectivecompositions also comprise treating surfaces of huts and houses, airspraying and impregnation of curtains, tents, clothing items, bed nets,tsetse-fly trap or the like. Insecticidal compositions for applicationto fibers, fabric, knitgoods, nonwovens, netting material or foils andtarpaulins preferably comprise a composition including the inventivemixtures, optionally a repellent and at least one binder.

The crystalline modification II, the mixtures and the compositionsaccording to the invention can be used for protecting wooden materialssuch as trees, board fences, sleepers, etc. and buildings such ashouses, outhouses, factories, but also construction materials,furniture, leathers, fibers, vinyl articles, electric wires and cablesetc. from ants and/or termites, and for controlling ants and termitesfrom doing harm to crops or human being (e.g. when the pests invade intohouses and public facilities).

In the case of soil treatment or of application to the pests dwellingplace or nest, the quantity of active ingredient ranges from 0.0001 to500 g per 100 m², preferably from 0.001 to 20 g per 100 m².

Customary application rates in the protection of materials are, forexample, from 0.01 g to 1000 g of active compound per m² treatedmaterial, desirably from 0.1 g to 50 g per m².

Insecticidal compositions for use in the impregnation of materialstypically contain from 0.001 to 95 weight %, preferably from 0.1 to 45weight %, and more preferably from 1 to 25 weight % of at least onerepellent and/or insecticide.

For use in bait compositions, the typical content of activeingredient(s) is from 0.0001 weight % to 15 weight %, desirably from0.001 weight % to 5% weight % of active compound. The composition usedmay also comprise other additives such as a solvent of the activematerial, a flavoring agent, a preserving agent, a dye or a bitteragent. Its attractiveness may also be enhanced by a special color, shapeor texture.

For use in spray compositions, the content of the active ingredient(s)is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % andmost preferably from 0.01 to 15 weight %.

For use in treating crop plants, the rate of application of the activeingredient(s) may be in the range of 0.1 g to 4000 g per hectare,desirably from 25 g to 600 g per hectare, more desirably from 50 g to500 g per hectare.

It was also an object of the present invention to provide mixturessuitable for treating, controlling, preventing and protectingwarm-blooded animals, including humans, and fish against infestation andinfection by pests. Problems that may be encountered with pest controlon or in animals and/or humans are similar to those described at theoutset, namely the need for reduced dosage rates, and/or enhancedspectrum of activity and/or combination of knock-down activity withprolonged control and/or resistance management.

This invention also provides a method for treating, controlling,preventing and protecting warm-blooded animals, including humans, andfish against infestation and infection by pests of the ordersSiphonaptera, Hymenoptera, Hemiptera, Orthoptera, Acarina, Phthiraptera,and Diptera, which comprises orally, topically or parenterallyadministering or applying to said animals a pesticidally effectiveamount of the crystalline modification II, the mixtures and thecompositions according to the invention.

The invention also provides a process for the preparation of acomposition for treating, controlling, preventing or protecting awarm-blooded animal or a fish against infestation or infection by pestsof the Siphonaptera, Hymenoptera, Hemiptera, Orthoptera, Acarina,Phthiraptera, and Diptera orders which comprises a pesticidallyeffective amount of the crystalline modification II, the mixtures andthe compositions according to the invention.

The above method is particularly useful for controlling and preventinginfestations and infections in warm-blooded animals such as cattle,sheep, swine, camels, deer, horses, poultry, goats, dogs and cats aswell as humans.

Infestations in warm-blooded animals and fish including, but not limitedto, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoidflies, flies, myiasitic fly larvae, chiggers, gnats, mosquitoes andfleas may be controlled, prevented or eliminated by the crystallinemodification II, the mixtures and the compositions according to theinvention.

For oral administration to warm-blooded animals, the crystallinemodification II, the mixtures and the compositions according to theinvention may be formulated as animal feeds, animal feed premixes,animal feed concentrates, pills, solutions, pastes, suspensions,drenches, gels, tablets, boluses and capsules. In addition, thecrystalline modification II, the mixtures and the compositions accordingto the invention may be administered to the animals in their drinkingwater. For oral administration, the dosage form chosen should providethe animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day ofthe crystalline modification II, the mixtures and the compositionsaccording to the invention.

Alternatively, the crystalline modification II, the mixtures and thecompositions according to the invention may be administered to animalsparenterally, for example, by intraruminal, intramuscular, intravenousor subcutaneous injection. The crystalline modification II, the mixturesand the compositions according to the invention may be dispersed ordissolved in a physiologically acceptable carrier for subcutaneousinjection. Alternatively, the crystalline modification II, the mixturesand the compositions according to the invention may be formulated intoan implant for subcutaneous administration. In addition, the crystallinemodification II, the mixtures and the compositions according to theinvention may be transdermally administered to animals. For parenteraladministration, the dosage form chosen should provide the animal with0.01 mg/kg to 100 mg/kg of animal body weight per day of the crystallinemodification II, the mixtures and the compositions according to theinvention.

The crystalline modification II, the mixtures and the compositionsaccording to the invention may also be applied topically to the animalsin the form of dips, dusts, powders, collars, medallions, sprays,spot-on and pour-on formulations. For topical application, dips andsprays usually contain 0.5 ppm to 5000 ppm and preferably 1 ppm to 3000ppm of the crystalline modification II. In addition, the crystallinemodification II may be formulated as ear tags for animals, particularlyquadrupeds such as cattle and sheep.

The figure and examples below serve to illustrate the invention and arenot to be understood as limiting it.

FIG. 1: X-ray powder diffractogram of modification II

FIG. 2: Differential scanning calorimetry thermogram of modification II

FIG. 3: Thermogravimetric analysis of modification II

FIG. 4: X-ray powder diffractograms of mixtures of modifications I and V

PREPARATION EXAMPLES Example 1 Characterization of a Solid Form ofFipronil as Starting Material

All preparation procedures below were conducted with two samples ofsolid fipronil as starting materials which were obtained according toprocedures as described in WO 2001/30760, with final crystallization ofthe product from a solvent mixture of MCB/ethanole (% by weight ofethanol at crystallization start: 13%) at temperatures of 70° C. to 35°C. This solid form in X-ray powder diffractogram studies proved to becrystalline fipronil of a mixture of several crystalline modifications.This mixture has been characterized to consist of crystallinemodification I and crystalline modification V, as for the first timeidentified and described in a co-pending patent application. A leastsquares refinement with the Topas program with simulated X-ray powderdiffractogram patterns from single crystal data of form I and form Vshows that in these two example samples, the percentage of form I variesfrom 30% to 70%. X-ray powder diffractograms of the two samples areshown in FIG. 4.

Irrespective of the sample of solid fipronil used as starting material,the crystallization examples given below yielded in modification II.

Example 2 Preparation of Modification II by Crystallization from THF

1.0 g of crystalline fipronil having a chemical purity of about 96% byweight was dissolved in 25 ml of THF at 45 to 50° C.[B7] in a roundbottomed flask. The solution was kept at this temperature while thesolvent was slowly evaporated with a gentle flow of inert N₂ gas. Thesolvent was left to evaporate for about 15 hours, after which theobtained crystalline material was filtered from some residual solvent ona paper filter. The material obtained has the X-ray powder diffractogramshown in FIG. 1 with the reflexes listed in Table 2 below.

Example 3 Preparation of Modification II by Crystallization from1,2-Dichloroethane (DCE)

1.0 g of crystalline fipronil having a chemical purity of about 96% byweight was dissolved in 25 ml of DCE at 45° C. to 50° C. in a roundbottomed flask. Then the heating was switched off and the oil bath wasleft to cool to 20° C. to 25° C. The solvent was left to evaporate forabout 15 hours. The material obtained has the X-ray powder diffractogramshown in FIG. 1 with the reflexes listed in Table 2 below.

Example 4 Preparation of Modification II by Crystallization fromAcetonitrile

2.0 g of crystalline fipronil having a chemical purity of about 96% byweight was dissolved in 4 ml of acetonitrile at 75° C. to 80° C. in a 10ml test tube to give a clear solution. The solution was cooled down to5° C. in approximately 8 h and left at 5° C. over night. The supernatantwas removed by using a pipet. The solid was dried on a filter paper fora few hours and then analyzed to give within a 0.3° 2θ error marginalthe X-ray powder diffractogram shown in FIG. 1.

Example 5 Preparation of Modification II by Crystallization from Toluene

0.7 g of fipronil having chemical purity of >98% by weight was suspendedin 10 ml of toluene in a 30 ml glass reactor. Stirring was applied andthe suspension was heated up to 110° C. where the solid was completelydissolved. The solution was then cooled down to 25° C. with a coolingrate of −1 K/min. The crystallization was observed to begin at 86° C.The solid product was filtrated and dried on filtration paper over nightand then analyzed to give within a 0.3° 2θ error marginal the X-raypowder diffractogram shown in FIG. 1. The content of fipronil in thisexperiment was 8.2 w-%.

Example 6 Preparation of Modification II by Crystallization fromMonochlorobenzene (MCB)

0.60 g of fipronil having chemical purity of >98% by weight wassuspended in 15 ml of MCB. Stirring was applied and the suspension washeated up to 137° C. where the solid was completely dissolved. Thesolution was then cooled down to 25° C. with a cooling rate of −1 K/min.The crystallization was observed to begin at 76° C. The solid productwas filtrated and dried on filtration paper over night and then analyzedto give within a 0.3° 2θ error marginal the X-ray powder diffractogramshown in FIG. 1.

Example 7 Preparation of Modification II by Crystallization fromMesitylene

2 g of fipronil having chemical purity of ˜96% by weight was dissolvedat 15 ml of mesitylene. The solution was cooled down within 5 hours to20-25° C. and left to stand over night. The crystallized solid wasfiltered and dried in a vacuum oven (at 10 mbar) for ˜1.5 h at 40° C.The sample was analyzed to give within a 0.3° 2θ error marginal theX-ray powder diffractogram shown in FIG. 1[B8].

Example 8 Preparation of Modification II by Crystallization fromNitrobenzene

2 g of fipronil having chemical purity of about 96% by weight wasdissolved at 5 ml of nitrobenzene. The solution was cooled down within 5hours to 20-25° C. and left to stand over night. The crystallized solidwas filtered and dried in a vacuum oven (at 10 mbar) for about 1.5 h at40° C. The sample was analyzed to give within a 0.3° 2θ error marginalthe X-ray powder diffractogram shown in FIG. 1[B9].

Example 9 Preparation of Modification II by Crystallization from EthylBenzene

1.5 g of fipronil having chemical purity of >98% by weight was suspendedin 10 ml of ethyl benzene. Stirring was applied and the suspension washeated up to 136° C. giving a clear solution. The solution was cooleddown to 25° C. with a cooling rate of −1 K/min. The crystallization wasdetected to begin at 118° C. The solid product was filtrated and driedon filtration paper over night and then analyzed to give within a 0.3°2θ error marginal the X-ray powder diffractogram shown in FIG. 1.

Example 10 Preparation of Modification II by Crystallization fromCF₃-Benzene

1.5 g of fipronil having chemical purity of >98% by weight was suspendedin 18.5 ml of CF₃-benzene. Stirring was applied and the suspension washeated up to 103° C. giving a clear solution. The solution was cooleddown to 25° C. with a cooling rate of −1 K/min. The crystallization wasdetected to begin at 97° C. The solid product was filtrated and dried onfiltration paper over night at 20-25° C. The sample was analyzed to bewithin 0.3° 2θ error marginal the X-ray powder diffractogram shown inFIG. 1.

TABLE 2 d-spacings and 2θ-angles of modification II d (Å) 2θ d = 13.44 ±0.2 Å  6.6 ± 0.2° d = 7.84 ± 0.1 Å 11.3 ± 0.2° d = 5.50 ± 0.07 Å 16.1 ±0.2° d = 5.14 ± 0.05 Å 17.2 ± 0.2° d = 4.95 ± 0.05 Å 17.9 ± 0.2° d =3.95 ± 0.05 Å 22.4 ± 0.2° d = 3.77 ± 0.05 Å. 23.5 ± 0.2° d = 3.22 ± 0.03Å 27.6 ± 0.2° d = 2.91 ± 0.03 Å 30.8 ± 0.2°

Analysis:

The X-ray powder diffractogram displayed in FIG. 1 was recorded using aSiemens D-5000 diffractometer (manufacturer: Bruker AXS) in reflectiongeometry in the range from 2θ=2°-60° with increments of 0.02° usingCu-Kα radiation at 25° C. The 2θ values found were used to calculate thestated interplanar spacing d. In FIG. 1, the intensity of the peaks(y-axis: linear intensity in counts) is plotted versus the 2θ angle(x-axis in degrees 2θ).

The single crystal X-ray diffraction data was collected on a Bruker AXSCCD Detector using graphite Cu_(Kα) radiation. The structure was solvedby using direct methods, refined, and expanded by using Fouriertechniques with the SHELX software package (G.M. Sheldrick, SHELX-97,Universitát Góttingen, 1997). Absorption correction was performed withSADABS software.

Melting points indicated herein refer to values determined on a Mettlerhot stage microscope and represent equilibrium melting points.

DSC was performed on a Mettler Toledo DSC 823 module in air atmosphere.Crystals taken from the mother liquor were blotted dry on filter paperand place in crimped but vented aluminum sample pans for the DCSexperiment. The sample size in each case was 5 to 10 mg. The temperaturerange was typically 30° C. to 230° C. at a heating rate of 5° C./min.

TGA measurements were performed on a SEIKO Instrument in nitrogenatmosphere in platinum pans. The sample size in each case was ˜8-10 mg.The temperature range was 30° C. to 600° C. at a heating rate 10°C./min.

Investigations of the effect of the temperature of nucleation andbeginning of the crystallization to the modification of the crystallineend product carried out with Polyblock by HEL Ltd. The multi reactorcrystallization system allows the monitoring of the crystallizationprocess and change in turbidity with special reflectance turbidityprobes by HEL. The heating/cooling mantle and thermostat “Julabo FP 50”as well as the turbidity probes were controlled with a PC.

1-27. (canceled)
 28. A crystalline modification II of fipronil which hasan X-ray powder diffractogram showing, at 25° C., at least 5 of thefollowing reflexes: (1) d=13.44±0.2 Å (2) d=7.84±0.1 Å (3) d=5.50±0.07 Å(4) d=5.14±0.05 Å (5) d=4.95±0.05 Å (6) d=3.95±0.05 Å (7) d=3.77±0.05 Å(8) d=3.22±0.03 Å (9) d=2.91±0.03 Å.
 29. The crystalline modification IIaccording to claim 28, wherein said modification undergoes a phasetransformation at 105° C. to 145° C. into two other crystallinemodifications I and V of fipronil having melting points at 196 to 197°C. and at 202 to 203° C., respectively.
 30. The crystalline modificationII of claim 28 having a fipronil content of at least 98% by weight. 31.A solid fipronil comprising the crystalline modification II of claim 28and a form of fipronil being different from crystalline modification II.32. The solid fipronil of claim 31, comprising the crystallinemodification II in at least 85% by weight.
 33. A process for preparingthe crystalline modification II of claim 30, comprising: i) preparing asolution of a solid form of fipronil being different from thecrystalline modification II in a solvent S selected from tetrahydrofuranand 1,2-dichloroethane; ii) effecting crystallization of fipronil; andiii) isolating the resulting precipitate.
 34. The process according toclaim 33, wherein the solvent S is tetrahydrofuran.
 35. The processaccording to claim 33, wherein the solvent S is 1,2-dichloroethane. 36.The process according to claim 33, wherein, in step ii), thecrystallization of fipronil is effected by concentration of the solutionobtained in step i).
 37. The process according to claim 33, wherein, instep ii), the crystallization of fipronil is effected by adding asolvent which reduces the solubility.
 38. The process according to claim33, wherein step ii) is carried out in the presence of seed crystals ofthe crystalline modification.
 39. A synergistic pesticidal orparasiticidal mixture comprising, as active components, the crystallinemodification II of claim 33 and one or more pesticidal or parasiticidalcompounds.
 40. The pesticidal or parasiticidal mixture of claim 39,further comprising a pesticidally or parasiticidally acceptable carrierand/or an auxiliary.
 41. The mixture of claim 40 in the form of anaqueous suspension concentrate.
 42. The mixture of claim 40 in the formof water-dispersible granules.
 43. The mixture of claim 40 in the formof a water-dispersible powder.
 44. A method for controlling pests whichcomprises contacting the pests or their food supply, habitat, breedinggrounds or their locus with a pesticidally effective amount of thecrystalline modification II of claim
 28. 45. The method of claim 44,wherein the crystalline modification II is applied in an amount of from5 g/ha to 2000 g/ha.
 46. A method for protecting a plant frominfestation and attack by pests which comprises applying to the foliageor stem of said plant a pesticidally effective amount of the crystallinemodification II of claim
 28. 47. The method of claim 49, wherein thecrystalline modification II is applied in an amount of from 5 g/ha to2000 g/ha.
 48. A method for the protection of seed comprising contactingthe seed with the crystalline modification II of claim
 28. 49. Themethod as claimed in claim 48, wherein the crystalline modification IIis applied in an amount of from 0.1 g to 10 kg per 100 kg of seeds. 50.A seed comprising the crystalline modification II of claim 28 in anamount of from 0.1 g to 10 kg per 100 kg of seeds.
 51. A method fortreating, controlling, preventing or protecting animals againstinfestation or infection by parasites which comprises orally, topicallyor parenterally administering or applying to the animals aparasiticidally effective amount of the crystalline modification II ofclaim 28.